KR20160106643A - Metal complex and light emitting element using same - Google Patents

Abstract

[식 중, M은 이리듐 원자 또는 백금 원자를 나타냄. n₁은 1, 2 또는 3을 나타냄. n₂는 0, 1 또는 2를 나타냄. E¹ 내지 E⁴는 질소 원자 또는 탄소 원자를 나타냄. R¹ 내지 R¹⁰은 수소 원자, 알킬기, 시클로알킬기, 알콕시기, 시클로알콕시기, 아릴기, 아릴옥시기, 1가의 복소환기 또는 할로겐 원자를 나타냄. R¹ 내지 R⁴로 이루어지는 군에서 선택되는 적어도 하나는 식 (D-A) 또는 (D-B)로 표현되는 기임. X^a 및 X^b는 직접 결합, 산소 원자, 황 원자, -C(=O)-, -CR^Xa ₂- 또는 -NR^Xa-를 나타냄. R^Xa는 수소 원자, 알킬기, 시클로알킬기, 아릴기 또는 1가의 복소환기를 나타냄. 단, X^a 및 X^b 중 적어도 한쪽은 산소 원자, 황 원자, -C(=O)-, -CR^Xa ₂- 또는 -NR^Xa-임. A¹-G¹-A²는 음이온성의 2좌 배위자를 나타내고, G¹은 A¹ 및 A²와 함께 2좌 배위자를 구성하는 원자단을 나타냄. A¹ 및 A²는 탄소 원자, 산소 원자 또는 질소 원자를 나타냄.]

[식 중, m^DA1 내지 m^DA7은 0 이상의 정수를 나타냄. G^DA는 방향족 탄화수소기 또는 복소환기를 나타냄. Ar^DA1 내지 Ar^DA7은 아릴렌기 또는 2가의 복소환기를 나타냄. T^DA는 아릴기 또는 1가의 복소환기를 나타냄.]A metal complex represented by the formula (1).

Wherein M represents an iridium atom or a platinum atom. n ₁ represents 1, 2 or 3; n ₂ represents 0, 1 or 2; E ¹ to E ⁴ represent a nitrogen atom or a carbon atom. R ¹ to R ¹⁰ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom. At least one selected from the group consisting of R ¹ to R ⁴ is a group represented by formula (DA) or (DB). X ^a and X ^b represent a direct bond, an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Xa ₂ - or -NR ^Xa -. R ^Xa represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. Provided that at least one of X ^a and X ^b is an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Xa ₂ - or -NR ^Xa -. A ¹ -G ¹ -A ² represents an anionic two-dimensional ligand, and G ¹ together with A ¹ and A ² represents an atomic group constituting a two-dimensional ligand. A ¹ and A ² represent a carbon atom, an oxygen atom or a nitrogen atom.

[ ^Wherein m ^DA1 to m ^DA7 represent an integer of 0 or more. ^GDA represents an aromatic hydrocarbon group or a heterocyclic group. Ar ^DA1 to Ar ^{DA7 each} represent an arylene group or a divalent heterocyclic group. ^TDA represents an aryl group or a monovalent heterocyclic group.]

Description

METAL COMPLEX AND LIGHT EMITTING ELEMENT USING SAME [0002]

The present invention relates to a metal complex, a composition containing the metal complex, and a light emitting device containing the metal complex.

As a luminescent material for use in the luminescent layer of the luminescent device, various phosphorescent luminescent compounds exhibiting luminescence from the triplet excited state have been studied variously. As the phosphorescent compound, a large number of metal complexes having a transition metal belonging to the 5th or 6th cycle of the central metal have been studied. For example, Patent Document 1 proposes a metal complex (for example, a metal complex represented below) having a phenylpyridine structure having a dendron as a ligand.

Japanese Patent Application Laid-Open No. 2011-105701

However, the quantum yield (hereinafter also referred to as " PLQY ") of the metal complex described in Patent Document 1 was not sufficient. Further, the half-value width of the luminescence spectrum of the metal complex described in Patent Document 1 was not sufficiently narrow.

Accordingly, an object of the present invention is to provide a metal complex excellent in quantum yield and excellent in half width of luminescence spectrum. The present invention also aims to provide a composition containing the metal complex and a light emitting element obtained using the metal complex.

The present invention first provides a metal complex represented by the following formula (1).

[Wherein,

M represents an iridium atom or a platinum atom.

n ₁ represents 1, 2 or 3; n ₂ represents 0, 1 or 2; When M is an iridium atom, n ₁ + n ₂ is 3, and when M is a platinum atom, n ₁ + n ₂ is 2.

E ¹ , E ² , E ³ and E ⁴ each independently represent a nitrogen atom or a carbon atom. When there are a plurality of E ¹ , E ² , E ³ and E ⁴ , they may be the same or different. When E ¹ is a nitrogen atom, R ¹ does not exist, and when E ² is a nitrogen atom, R ² does not exist. When E ³ is a nitrogen atom, R ³ does not exist and E ⁴ When it is a nitrogen atom, R ⁴ does not exist.

^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9 and R ¹⁰ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl An aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent. When there are a plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , they may be the same or different. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ^8, and R ⁸ and R ⁹ are each bonded to form a It may form a ring together with an atom. Provided that at least one group selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ is a group represented by the following formula (DA) or (DB).

X ^a and X ^b each independently represent a direct bond, an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Xa ₂ - or NR ^Xa -. R ^Xa represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of R ^Xa , they may be the same or different and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. When ^a plurality of X ^a and X ^b are present, they may be the same or different. Provided that at least one of X ^a and X ^b is an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Xa ₂ - or -NR ^Xa -.

A ¹ -G ¹ -A ² represents an anionic two-dimensional ligand, and G ¹ together with A ¹ and A ² represents an atomic group constituting a two-dimensional ligand. A ¹ and A ² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. When a plurality of A ¹ -G ¹ -A ² exist, they may be the same or different.]

[Wherein,

m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.

^GDA represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.

Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When there are a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , they may be the same or different.

^TDA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. Multiple ^TTAs present may be the same or different.]

[Wherein,

m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more.

^GDA represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent. Multiple ^GDAs may be the same or different.

Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When Ar ^{DA1, DA2} Ar, Ar ^{DA3, DA4} Ar, Ar ^{DA5, DA6} Ar and Ar ^DA7 a plurality is present, they each may be the same or different.

^TDA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. Multiple ^TTAs present may be the same or different.]

The present invention secondly provides a metal complex represented by the following formula (2).

[Wherein,

M represents an iridium atom or a platinum atom.

n ₁ represents 1, 2 or 3; n ₂ represents 0, 1 or 2; When M is an iridium atom, n ₁ + n ₂ is 3, and when M is a platinum atom, n ₁ + n ₂ is 2.

E ¹ , E ² , E ³ and E ⁴ each independently represent a nitrogen atom or a carbon atom. When there are a plurality of E ¹ , E ² , E ³ and E ⁴ , they may be the same or different. When E ¹ is a nitrogen atom, R ¹¹ is absent. When E ² is a nitrogen atom, R ¹² does not exist. When E ³ is a nitrogen atom, R ¹³ does not exist and E ⁴ When it is a nitrogen atom, R < ¹⁴ > does not exist.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, An aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent. When a plurality of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are present, they may be the same or different. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ^8, and R ⁸ and R ⁹ are bonded to each other to form a It may form a ring together with an atom.

Y ^a and Y ^b each independently represent a direct bond, an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Ya R ^Yb - or -NR ^Yc -. R ^Ya represents an alkyl group or a cycloalkyl group, and these groups may have an aryl group or a monovalent heterocyclic group as a substituent. R ^Yb represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. R ^Yc represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. Provided that at least one of Y ^a and Y ^b is -CR ^Ya R ^Yb -.

A ¹ -G ¹ -A ² represents an anionic two-dimensional ligand, and G ¹ together with A ¹ and A ² represents an atomic group constituting a two-dimensional ligand. A ¹ and A ² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. When a plurality of A ¹ -G ¹ -A ² exist, they may be the same or different.]

Third, the present invention provides a composition containing the above metal complex.

Fourth, the present invention provides a light emitting device obtained by using the metal complex.

According to the present invention, it is possible to provide a metal complex excellent in quantum yield and excellent in half width of the luminescence spectrum. Further, according to the present invention, it is possible to provide a composition containing the metal complex and a light emitting device obtained using the metal complex. Since the metal complex of the present invention has excellent quantum yield, the light emitting element obtained using the metal complex is excellent in external quantum efficiency. Further, since the metal complex of the present invention has a good half-width of the emission spectrum, when a light emitting element obtained by using the metal complex is used in combination with a color filter, and the cavity of the light emitting element obtained using the metal complex is adjusted , Its external quantum efficiency becomes even better.

1 is an emission spectrum of the metal complex M1, metal complex M2 and metal complex CM1.
2 is a diagram showing the transmission spectrum of the color filter used in the embodiment.

Hereinafter, preferred embodiments of the present invention will be described in detail.

<Description of common terms>

Hereinafter, terms commonly used in the present specification have the following meanings unless otherwise specified.

Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.

In the present specification, the hydrogen atom may be a deuterium atom or an oxygen atom.

In the present specification, in the structural formulas representing the metal complexes, the solid line indicating the bond with the central metal means a covalent bond or a coordination bond.

Means a polymer having a molecular weight distribution and having a number average molecular weight in terms of polystyrene of 1 x 10 ³ to 1 x 10 ⁸ . The total amount of the constituent units contained in the polymer compound is 100 mol%.

The polymer compound may be any of block copolymers, random copolymers, alternating copolymers and graft copolymers, and may be in any other form.

The terminal group of the polymer compound is preferably a stable group because the polymerization activity is left intact when the polymer compound is used for the production of a light emitting device because the light emitting property and the luminance lifetime may be lowered. As the terminal group, a group conjugated with the main chain is preferable, and a group bonded to an aryl group or a monovalent heterocyclic group through a carbon-carbon bond.

Means a compound having no molecular weight distribution and having a molecular weight of 1 x 10 ⁴ or less.

The term &quot; constituent unit &quot; means a unit in which at least one is present in the polymer compound.

The &quot; alkyl group &quot; may be any of linear or branched. The number of carbon atoms of the straight-chain alkyl group does not include the number of carbon atoms of the substituent and is usually 1 to 50, preferably 3 to 30, more preferably 4 to 20. The number of carbon atoms of the branched alkyl group does not include the number of carbon atoms of the substituent, and is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20.

The number of carbon atoms in the &quot; cycloalkyl group &quot; does not include the number of carbon atoms of the substituent, and is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20.

The alkyl group and cycloalkyl group may have a substituent, and examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, , A hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a 3-propylheptyl group, a decyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, Hexyl group, and groups in which hydrogen atoms in these groups are substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom and the like, and examples of the alkyl group and cycloalkyl group having a substituent include trifluoro A perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, a 3- (4-methylphenyl) propyl group, a 3- -Hexylphenyl) propyl group, a 6-ethyloxyhexyl group, a cyclohexylmethyl group, and a cyclohexylethyl group .

The "aryl group" means an atomic group remaining in an aromatic hydrocarbon excluding one hydrogen atom directly bonded to a carbon atom constituting the ring. The number of carbon atoms of the aryl group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 20, more preferably 6 to 10.

The aryl group may have a substituent, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, Fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and the hydrogen atoms in these groups may be substituted with an alkyl group, a cycloalkyl group, An alkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom and the like.

The &quot; alkoxy group &quot; may be any of linear or branched. The number of carbon atoms of the straight-chain alkoxy group does not include the number of carbon atoms of the substituent, and is usually 1 to 40, preferably 4 to 10. The number of carbon atoms of the alkoxy group of the branch does not include the number of carbon atoms of the substituent, and is usually 3 to 40, preferably 4 to 10.

The number of carbon atoms in the &quot; cycloalkoxy group &quot; does not include the number of carbon atoms in the substituent group, and is usually 3 to 40, preferably 4 to 10.

The alkoxy group and the cycloalkoxy group may have a substituent, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a tert- Hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group.

The number of carbon atoms of the &quot; aryloxy group &quot; does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 7 to 48.

The aryloxy group may have a substituent, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, Group in which a hydrogen atom is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom, or the like.

The "p-valent heterocyclic ring" (p represents an integer of 1 or more) means a remaining atomic group in the heterocyclic compound excluding the p hydrogen atoms of the hydrogen atoms directly bonded to the carbon atom or the hetero atom constituting the ring . Of the aromatic heterocyclic compounds of the p-valent heterocyclic group, the "p-valent aromatic heterocyclic group", which is the remaining atom except the p hydrogen atoms of the hydrogen atoms directly bonded to the carbon atom constituting the ring or the hetero atom, is preferable.

The term "aromatic heterocyclic compound" refers to an aromatic heterocyclic compound which may be substituted with at least one of oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phospholane, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, Compounds in which the heterocycle itself exhibits aromaticity, such as benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiophene, &Lt; / RTI &gt; wherein the aromatic ring is cyclic.

The number of carbon atoms of the monovalent heterocyclic group does not include the number of carbon atoms of the substituent, and is usually 2 to 60, preferably 4 to 20.

The monovalent heterocyclic group may have a substituent and includes, for example, thienyl, pyrrolyl, furyl, pyridyl, piperidyl, quinolyl, isoquinolyl, pyrimidinyl, Group in which a hydrogen atom is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or the like.

The "halogen atom" represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The "amino group" may have a substituent, and a substituted amino group is preferable. The substituent of the amino group is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group.

Examples of the substituted amino group include a dialkylamino group, a dicycloalkylamino group and a diarylamino group.

Examples of the amino group include a dimethylamino group, a diethylamino group, a diphenylamino group, a bis (4-methylphenyl) amino group, a bis (4-tert- .

The &quot; alkenyl group &quot; may be either straight or branched. The number of carbon atoms of the straight chain alkenyl group does not include the number of carbon atoms of the substituent, and is usually 2 to 30, preferably 3 to 20. The number of carbon atoms of the alkenyl group of the branch does not include the number of carbon atoms of the substituent, and is usually 3 to 30, preferably 4 to 20.

The number of carbon atoms in the &quot; cycloalkenyl group &quot; does not include the number of carbon atoms in the substituent group, and is usually 3 to 30, preferably 4 to 20.

The alkenyl group and the cycloalkenyl group may have a substituent, and examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, 1-hexenyl group, 5-hexenyl group, 7-octenyl group, and groups in which these groups have a substituent.

The &quot; alkynyl group &quot; may be either linear or branched. The number of carbon atoms of the alkynyl group does not include the carbon atom of the substituent, and is usually 2 to 20, preferably 3 to 20. The number of alkynyl group carbon atoms in the branch does not include the carbon atom of the substituent group, and is usually 4 to 30, preferably 4 to 20.

The number of carbon atoms of the "cycloalkynyl group" does not include the carbon atom of the substituent, and is usually 4 to 30, preferably 4 to 20.

The alkynyl group and the cycloalkynyl group may have a substituent, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, A 1-hexynyl group, a 5-hexynyl group, and a group having a substituent group.

"Arylene group" means an atomic group remaining in an aromatic hydrocarbon excluding two hydrogen atoms directly bonded to a carbon atom constituting a ring. The number of carbon atoms of the arylene group does not include the number of carbon atoms of the substituent, and is usually from 6 to 60, preferably from 6 to 30, and more preferably from 6 to 18.

The arylene group may have a substituent, and examples thereof include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenyl group, a dihydrophenanthrene diyl group, a naphthacenediyl group, a fluorenediyl group, a pyrandiyl group, , A chrysene dianion group, and a group having these groups having a substituent, and is preferably a group represented by formulas (A-1) to (A-20). The arylene group includes groups in which these groups are bonded in plural.

Wherein R and R ^a each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R and R ^a present may be the same or different and each R ^a may be bonded to each other to form a ring together with the atoms to which they are bonded.

The number of carbon atoms of the divalent heterocyclic group does not include the number of carbon atoms of the substituent, and is usually from 2 to 60, preferably from 3 to 20, and more preferably from 4 to 15.

The divalent heterocyclic group may have a substituent and may include substituents such as pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, In which two hydrogen atoms of a hydrogen atom directly bonded to a carbon atom or a heteroatom constituting the ring are excluded in the phenothiazine, acridine, dihydraacridine, furan, thiophene, azole, diazole and triazole A bivalent group, and is preferably a group represented by formulas (AA-1) to (AA-34). The divalent heterocyclic group includes groups in which these groups are bonded in plural.

[Wherein R and R ^a have the same meanings as defined above].

(B-1), (B-2), (B-3) and (B-3) is a group capable of forming a new bond by providing a heat treatment, an ultraviolet ray irradiation treatment, , B-4, B-5, B-6, B-7, B-8, B-9, B- B-12), (B-13), (B-14), (B-15), (B-16) or (B-17).

[Wherein, these groups may have a substituent]

"Substituent group" means a group selected from the group consisting of halogen atom, cyano group, alkyl group, cycloalkyl group, aryl group, monovalent heterocyclic group, alkoxy group, cycloalkoxy group, aryloxy group, amino group, substituted amino group, alkenyl group, cycloalkenyl group, Cycloalkynyl group. The substituent may be a crosslinking group.

The term &quot; dendron &quot; is a group having a regular dendritic structure (dendrimer structure) having atoms or rings as branch points. Examples of the compound having a dendron as a partial structure (sometimes referred to as a dendrimer) include structures described in WO 02/067343, JP 2003-231692, WO 2003/079736, WO 2006/097717, etc. have. A group represented by the formula (D-A) and a group represented by the formula (D-B).

m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are usually an integer of 10 or less, preferably an integer of 5 or less, more preferably 0 or 1, desirable. It is also preferable that m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are the same integer.

G ^DA is a group represented by the formula preferably (GDA-11) to (GDA-15), these groups may have a substituent.

[Wherein,

* Indicates the bond of Ar Ar ^{DA2 DA3} in the, or a group represented by the formula (DB) of the Ar ^DA1, formula (DB) of the Ar ^DA1, formula (DB) in the equation (DA).

** indicates the binding of Ar ^DA6 in ^DA4 Ar, or a group represented by the formula (DB) of the Ar ^DA2, formula (DB) of the Ar ^DA2, formula (DB) in the equation (DA).

*** indicates the combination of Ar ^DA7 in ^DA5 Ar, or a group represented by the formula (DB) of the Ar ^DA3, formula (DB) of the Ar ^DA3, formula (DB) in the equation (DA).

R ^DA represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may also have a substituent. When ^RDA is plural, they may be the same or different.]

^RDA is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and these groups may have a substituent.

Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 are preferably groups represented by formulas (ArDA-1) to (ArDA-3).

[Wherein,

R ^DA has the same meaning as above.

R ^DB represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are plural R ^DBs , they may be the same or different.]

R ^DB is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group or a monovalent heterocyclic group, and more preferably an aryl group.

T ^DA is a group which is preferably represented by formula (TDA-1) to (TDA-3).

[ ^Wherein R ^DA and R ^DB have the same meanings as defined above].

The group represented by the formula (D-A) is preferably a group represented by the formula (D-Al) to (D-A3).

[Wherein,

R ^p1 , R ^p2 and R ^p3 each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When there are plural R ^p1 and R ^p2 , they may be the same or different.

np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. Multiple np1 may be the same or different.]

The group represented by the formula (D-B) is preferably a group represented by the formula (D-B1) to (D-B3).

[Wherein,

R ^p1 , R ^p2 and R ^p3 each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When there are plural R ^p1 and R ^p2 , they may be the same or different.

np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. When np1 and np2 are plural, they may be the same or different.]

np1 is preferably 0 or 1, more preferably 1. np2 is preferably 0 or 1, more preferably 0. np3 is preferably zero.

R ^p1 , R ^p2 and R ^p3 are preferably an alkyl group or a cycloalkyl group.

<Metal Complex>

Next, the metal complex of the present invention will be described. The metal complex of the present invention is represented by Formula (1) or Formula (2).

The metal complex represented by the formula (1) has a group represented by the formula (D-A) or (D-B).

At least one group selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ is a group represented by the formula (DA) or (DB), R ¹ , R ² , R ³ and R when ^four multiple presence, respectively, of at least one of them is formula (DA), or if the group represented by (DB), but all of R ² to all of the plurality present in the R ^1, which plurality is present, a plurality existence R ³ to Or all of R &lt; ⁴ &gt; which are present in whole or in plurality are groups represented by formula (DA) or (DB).

In the formula (1), at least one selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ is preferably a group represented by the formula (DA) since the quantum yield of the metal complex of the present invention is more excellent , A group represented by the formula (D-A1), (D-A2) or (D-A3), and more preferably a group represented by the formula (D-A3).

In the formula (1), R ² is preferably a group represented by the formula (DA) or (DB), more preferably a group represented by the formula (DA) since the quantum yield of the metal complex of the present invention is better , A group represented by the formula (D-A1), (D-A2) or (D-A3), and particularly preferably a group represented by the formula (D-A3).

Formula (1) of, R ^1, R ^2, if a group other than a group represented R ³ and R ⁴ have the formula (DA), or (DB), R ^1, R ^2, R ³ and R ⁴ of the present invention It is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, Is more preferable.

Formula (1) of, X is ^a direct bond, an oxygen atom, a sulfur atom, -CR ^Xa ₂ - or -NR ^Xa - which is preferred, a direct bond or -CR ^Xa ₂ - is more preferable that, ^Xa and -CR ₂ -. &Lt; / RTI &gt;

In formula (1), X ^b is preferably a direct bond, an oxygen atom, a sulfur atom, -CR ^Xa ₂ - or -NR ^Xa -, more preferably a direct bond or -CR ^Xa ₂ - Is more preferable.

Provided that at least one of X ^a and X ^b is an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Xa ₂ - or -NR ^Xa -.

Formula (1), the combination of X ^a and X ^b is because it is better than the quantum yield of the metal complex of the present invention,

A combination wherein X ^a is -CR ^Xa ₂ - and X ^b is a direct bond, X ^a is -CR ^Xa ₂ - and X ^b is -NR ^Xa -, X ^a is an oxygen atom and X ^b is a direct bond, X ^a is an oxygen atom and X ^b is -NR ^Xa - combination, X is ^a sulfur atom and X ^b is a combination of a direct bond, X is ^a -C (= O) -, and X ^b is a direct bond in combination, X ^a combination in which ^a is -NR ^{X a} - and X ^b is a direct bond, X ^a is a direct bond and X ^b is -CR ^Xa ₂ -, or a combination in which X ^a is a direct bond and X ^b is a sulfur atom ,

A combination wherein X ^a is -CR ^Xa ₂ - and X ^b is a direct bond, or ^a combination in which X ^a is a direct bond and X ^b is -CR ^Xa ₂ -

More preferably X ^a is -CR ^Xa ₂ - and X ^b is a direct bond,

X ^a represents -CR ^Xb R ^Xc - (wherein R ^Xb represents an alkyl group or a cycloalkyl group, these groups may have an aryl group or a monovalent heterocyclic group as a substituent, R ^Xc represents an aryl group or a monovalent heterocyclic group, These groups may have substituents) and X ^b is a direct bond.

In the formula (1), R ^Xa is preferably an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and is more preferably an alkyl group or an aryl group because the luminescent element using the metal complex of the present invention has excellent luminance lifetime .

In the formula (1), R ^Xb is preferably an alkyl group because the luminescent element using the metal complex of the present invention has excellent luminance lifetime.

In the formula (1), R ^Xc is preferably an aryl group, and more preferably a phenyl group, since the luminescent device using the metal complex of the present invention has excellent luminance lifetime.

In the metal complex represented by the formula (2), at least one of Y ^a and Y ^b is -CR ^Ya R ^Yb -.

When ^a plurality of Y ^a and Y ^b are present in the formula (2), at least one of them may be -CR ^Ya R ^Yb -, but all of ^a plurality of Y ^a or a plurality of Y ^b , CR ^Ya R ^Yb -.

In formula (2), Y ^a is preferably a direct bond, an oxygen atom, a sulfur atom, -CR ^Ya R ^Yb - or -NR ^Yc -, more preferably a direct bond or -CR ^Ya R ^Yb - CR ^Ya R ^Yb -.

In formula (2), Y ^b is preferably a direct bond, an oxygen atom, a sulfur atom, -CR ^Ya R ^Yb - or -NR ^Yc -, more preferably a direct bond or -CR ^Ya R ^Yb - Bond.

Provided that at least one of Y ^a and Y ^b is -CR ^Ya R ^Yb -.

In the formula (2), the combination of Y ^a and Y ^b is more excellent in the quantum yield of the metal complex of the present invention,

A combination wherein Y ^a is -CR ^Ya R ^Yb - and Y ^b is a direct bond, Y ^a is -CR ^Ya R ^Yb - and Y ^b is -NR ^Yc -, Y ^a is -CR ^Ya R ^Yb - and Y ^b A combination wherein Y ^a is -CR ^Ya R ^Yb - and Y ^b is a sulfur atom, Y ^a is a direct bond and Y ^b is -CR ^Ya R ^Yb -, Y ^a is -NR ^Yc - Y is -CR ^b R ^{Ya Yb} - combination, Y is ^a oxygen atom and Y is -CR ^b R ^{Ya Yb} - combination, or Y is ^a sulfur atom and Y is -CR ^b R ^{Ya Yb} - preferably is a combination of and,

A combination wherein Y ^a is -CR ^Ya R ^Yb - and Y ^b is a direct bond, or ^a combination in which Y ^a is a direct bond and Y ^b is -CR ^Ya R ^Yb -

Y ^a is -CR ^Ya R ^Yb - and Y ^b is a direct bond.

In the formula (2), R ^Ya is preferably an alkyl group which may have a substituent because the life of the light-emitting element using the metal complex of the present invention is excellent.

In the formula (2), R ^Yb is preferably an aryl group which may have a substituent, and is more preferably a phenyl group which may have a substituent because the luminous element using the metal complex of the present invention has a superior luminance lifetime.

In the formula (2), at least one selected from the group consisting of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is more excellent in the quantum yield of the metal complex of the present invention, .

All of R ^11, R ^12, R ¹³ and R ¹⁴ are if multiple presence each, all of the all of the plurality present R ¹¹ all, a plurality existence R ¹² in which, for a plurality existence R ^13, or a plurality of existing R ¹⁴ Is preferably a group represented by the formula (DA) or (DB).

In the formula (2), at least one selected from the group consisting of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is preferably a group represented by the formula (DA) since the quantum yield of the metal complex of the present invention is more excellent , A group represented by the formula (D-A1), (D-A2) or (D-A3), and more preferably a group represented by the formula (D-A3).

In the formula (2), R ¹² is preferably a group represented by the formula (DA) or (DB) and more preferably a group represented by the formula (DA) since the quantum yield of the metal complex of the present invention is better. , More preferably a group represented by the formula (D-A1), (D-A2) or (D-A3) and particularly preferably a group represented by the formula (D-A3).

Formula (2) ^{of, R 11, R 12, R} 13 and R, if ¹⁴ is a group other than the group represented by formula (DA), or ^{(DB), R 11, R 12, R} 13 and R ¹⁴ are of the invention It is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, Is more preferable.

Among the formulas (1) and (2), M is preferably an iridium atom since the light emitting element using the metal complex of the present invention has excellent brightness lifetime.

In the formulas (1) and (2), n ₂ is preferably 0 since the luminosity of the light emitting device using the metal complex of the present invention is excellent.

E ¹ , E ² , E ³ and E ⁴ in the formulas (1) and (2) are preferably carbon atoms since the metal complexes of the present invention can be easily synthesized.

In the formulas (1) and (2), R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group Or a halogen atom, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, more preferably a hydrogen atom.

In the formulas (1) and (2), R ⁷ and R ⁸ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, It is preferably a halogen atom, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group.

Examples of the anionic two-coordinate ligand represented by A ¹ -G ¹ -A ² in the formulas (1) and (2) include, for example, ligands represented by the following formulas.

[Wherein * represents a site bonding with an iridium atom or a platinum atom]

In the formulas (1) and (2), an anionic two-terminal ligand represented by A ¹ -G ¹ -A ² may be a ligand represented by the following formula. However, an anionic ^two- terminal ligand represented by A ¹ -G ¹ -A ² is different from a ligand whose number is defined by subscript n ₁ .

[Wherein,

* Indicates a site bonding with an iridium atom or a platinum atom.

R ^L1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent. Plural R ^{L1 's} may be the same or different.

R ^L2 represents an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent.

Examples of the metal complex represented by the formula (1) or (2) include metal complexes represented by the following formulas (Ir-1) to (Ir-26). Ir-1, Ir-2, Ir-3, Ir-4, Ir-15 and Ir- (Ir-1), (Ir-2), (Ir-20), -3), (Ir-4), (Ir-15) or (Ir-16). Among them, metal complexes represented by the formulas (Ir-1), (Ir-2), (Ir-3) or (Ir-4) are more preferable, (Ir-1) or (Ir-3) is particularly preferable.

[Of the formulas (Ir-1) to (Ir-26)

R ^L5 represents an alkyl group, a cycloalkyl group, a halogen atom, an aryl group, a 1,3,5-triazin-2-yl group having a substituent at the 4-position and the 6-position, , 3-pyrimidin-2-yl group, or dendron. When there are plural R ^L5 , they may be the same or different.

R ^Za is a group represented by R ^Xa or R ^Ya , R ^Zb is a group represented by R ^Xa or R ^Yb , and R ^Zc is a group represented by R ^Xa or R ^Yc . Provided that when R ^Za is a group represented by R ^Xa , R ^Zb and R ^Zc are groups represented by R ^Xa , and when R ^Za is a group represented by R ^Ya , R ^Zb is a group represented by R ^Yb , and R ^Zc is a group represented by R ^Yc . When there are a plurality of R ^Za , they may be the same or different. When a plurality of R ^Zb exist, they may be the same or different. When a plurality of R ^Zc exist, they may be the same or different.

Z ^1a is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group represented by the formula (DA) or (DB). Provided that when R ^Za is a group represented by R ^Xa and R ^Zb is a group represented by R ^Xa , then Z ^1a is a group represented by formula (DA) or (DB). When there are plural Z ^{1a s} , they may be the same or different.]

Of the formulas (Ir-1) to (Ir-26)

R ^L5 is a group selected from the groups represented by the formulas (II-1) to (II-15) of the following Group II and the groups represented by the formulas (III-1) to (III-17) .

Z ^1a is preferably a group selected from groups represented by formulas (III-1) to (III-17) of Group III which is a group represented by the formula (DA)

<Group II>

<Group III>

Of the formulas (Ir-1) to (Ir-26), Z ^1a is preferably a group selected from the group consisting of groups represented by formulas (III-1) to (III-13) ) To (III-13).

As R ^Xa represented by R ^Za , R ^Zb or R ^Zc in the formulas (Ir-1) to (Ir-26), an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable, and an alkyl group, More preferably an aryl group, and these groups may have a substituent.

Of the formulas (Ir-1) to (Ir-26), as the R ^Ya represented by R ^Za , an unsubstituted alkyl group or an unsubstituted cycloalkyl group is preferable.

Of the formulas (Ir-1) to (Ir-26), as the R ^Yb represented by R ^Zb , an aryl group is preferable, and an aryl group having an alkyl group as a substituent is preferable.

Of the formulas (Ir-1) to (Ir-26), as R ^Yc represented by R ^Zc , an aryl group is preferable and an aryl group having an alkyl group as a substituent is preferable.

Examples of the metal complexes represented by the formula (1) or (2) include metal complexes represented by the following formulas (Ir-101) to (Ir-122).

A plurality of stereoisomers may exist in the metal complex represented by the formulas (1) and (2). For example, a metal complex having a ligand such as an enantiomer, a metal complex having a ligand as a diastereomer, and a metal complex having a plurality of ligands as an enantiomer, thereby forming a diastereomer as a whole.

Among metal complexes represented by the formulas (1) and (2), a metal complex in which M is an iridium atom and n ₂ is 0 may exist in the form of a facial form or a meridional form stereoisomer And the facial body is preferably 80 mol% or more, more preferably 90 mol% or more, and 99 mol% or more, based on the entire metal complex, since the half value width of the emission spectrum of the metal complex of the present invention is better , And more preferably 100 mol% (i.e., one not containing a meridional body) is particularly preferable.

In the light emitting device obtained by using the metal complex of the present invention, the metal complex of the present invention may be used singly or two or more of them may be used in combination.

<Method for producing metal complex represented by formula (1)

[Manufacturing Method 1]

The metal complex represented by the formula (1), which is a metal complex of the present invention, can be produced, for example, by a method of reacting a compound as a ligand with a metal compound. If necessary, the functional group conversion reaction of the ligand of the metal complex can be performed.

Among the metal complexes represented by the formula (1), when M is an iridium atom and n1 is 3, for example,

A step A1 of synthesizing a metal complex represented by the formula (M1-2) by reacting a compound represented by the formula (M1-1) with an iridium compound or a hydrate thereof; and

A step B1 of reacting a metal complex represented by the formula (M1-2) with a compound represented by the formula (M1-1) or a precursor of a ligand represented by A ¹ -G ¹ -A ² can do.

[Wherein E ¹ to E ⁴ , R ¹ to R ¹⁰ , X ^a and X ^b have the same meanings as defined above]

Examples of the iridium compound in the step A1 include iridium chloride, tris (acetylacetonato) iridium (III), chloro (cyclooctadiene) iridium (I) dimer and iridium (III) The hydrate of the compound includes, for example, iridium chloride-trihydrate.

Step A1 and step B1 are usually carried out in a solvent. Examples of the solvent include alcohols such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin, 2- methoxyethanol, 2- ethoxyethanol, 2- (2- ethoxyethoxy) Alcohol solvents such as ethanol, 2- (n-butoxy) ethanol and 2- (t-butoxy) ethanol; Ether solvents such as tetrahydrofuran, dioxane, cyclopentyl methyl ether and diglyme; Halogen-based solvents such as methylene chloride and chloroform; Nitrile solvents such as acetonitrile and benzonitrile; Hydrocarbon solvents such as hexane, decalin, toluene, xylene, and mesitylene; Amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; Acetone, dimethyl sulfoxide, and water.

In Process A1 and Process B1, the reaction time is usually 30 minutes to 150 hours, and the reaction temperature is usually between the melting point of the solvent present in the reaction system and the boiling point.

In the step A1, the amount of the compound represented by the formula (M1-1) is usually 2 to 20 moles per 1 mole of the iridium compound or its hydrate.

In the step B1, the amount of the precursor of the ligand represented by the formula (M1-1) or the ligand represented by A ¹ -G ¹ -A ² is usually 1 to 1 mol of the metal complex represented by the formula (M1-2) To 100 moles.

In the step B1, the reaction is preferably carried out in the presence of a silver compound such as trifluoromethanesulfonic acid. When a compound is used, the amount thereof is usually 2 to 20 moles per 1 mole of the metal complex represented by the formula (M1-2).

The compound represented by the formula (M1-1) can be prepared by, for example, reacting a compound represented by the formula (M1-3) and a compound represented by the formula (M1-4) with a Suzuki reaction, Reaction, Stille reaction, or the like.

[Wherein,

E ¹ to E ⁴ , R ⁵ to R ¹⁰ , X ^a and X ^b have the same meanings as defined above.

Z ¹ represents a group represented by the formula (DA) or (DB).

W ¹ represents a group represented by -B (OR ^W1 ) ₂ , an alkylsulfonyloxy group, a cycloalkylsulfonyloxy group, an arylsulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom, and these groups may have a substituent .

R ^1a, R ^2a, R ^3a and R ^4a are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, -B (OR ^W1) ₂ An alkylsulfonyloxy group, a cycloalkylsulfonyloxy group, an arylsulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom, and these groups may have a substituent. R ^1a and R ^2a , R ^2a and R ^3a , R ^3a and R ^4a , and R ^4a and R ⁵ may combine with each other to form a ring together with the atoms to which they are bonded. Provided that at least one selected from the group consisting of R ^1a , R ^2a , R ^3a and R ^4a is a group represented by -B (OR ^W1 ) ₂ , an alkylsulfonyloxy group, a cycloalkylsulfonyloxy group, an arylsulfonyloxy group, A chlorine atom, a bromine atom or an iodine atom.

R ^W1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an amino group, and these groups may have a substituent. Plural R ^{W1 s} may be the same or different and may combine with each other to form a cyclic structure together with the oxygen atom to which they are bonded.

Examples of the group represented by B (OR ^W1 ) ₂ include groups represented by the following formulas (W-1) to (W-10).

The alkylsulfonyloxy group represented by W ¹ includes, for example, a methanesulfonyloxy group, an ethanesulfonyloxy group, and a trifluoromethanesulfonyloxy group.

The arylsulfonyloxy group represented by W ¹ includes, for example, p-toluenesulfonyloxy group.

W ¹ is preferably a group represented by -B (OR ^W1 ) ₂ , a group represented by -B (OR ^W1 ) ₂ , a group represented by formula A chlorine atom, a bromine atom or an iodine atom is preferable. Among them, a compound represented by the formula (M1-4) is preferable since it is easy to synthesize a compound represented by the formula (M1-4) The value of g is more preferable.

The alkylsulfonyloxy, cycloalkylsulfonyloxy and arylsulfonyloxy groups represented by R ^1a to R ^4a have the same meanings as the alkylsulfonyloxy, cycloalkylsulfonyloxy and arylsulfonyloxy groups represented by W ¹ , respectively .

As R ^2a , a bromine atom, an iodine atom or a group represented by the formula (W-7) is preferable.

As Z ¹ , a group represented by the formula (DA) is preferable, and a group represented by the formula (D-A1) to the formula (D-A3) is more preferable.

The coupling reaction between the compound represented by the formula (M1-3) and the compound represented by the formula (M1-4) is usually carried out in a solvent. The solvent used, the reaction time and the reaction temperature are the same as those described for Process A1 and Process B1.

In the coupling reaction between the compound represented by the formula (M1-3) and the compound represented by the formula (M1-4), the amount of the compound represented by the formula (M1-4) And usually 0.05 to 20 moles per 1 mole of the compound.

Examples of the compound represented by the formula (M1-4) include a compound wherein Z ¹ is a group represented by the formula (D-A1) to (D-A3) and W ¹ is represented by -B (OR ^W1 ) ₂ Group, a trifluoromethanesulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom.

The compound represented by the formula (M1-4-1) which is one embodiment of the compound represented by the formula (M1-4) can be synthesized, for example, by the following method.

[Wherein,

R ^p1 and np1 have the same meanings as defined above.

W ² represents a group represented by -B (OR ^W1 ) ₂ , an alkylsulfonyloxy group, a cycloalkylsulfonyloxy group, an arylsulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom, and these groups may have a substituent .]

The compound represented by the formula (M1-4-1) can be produced, for example, by coupling reaction between a compound represented by the formula (M1-4-1a) and a compound represented by the formula (M1-4-1b) . This coupling reaction is the same as described for the compound represented by the formula (M1-1).

The compound represented by the formula (M1-4-2) which is one embodiment of the compound represented by the formula (M1-4) can be synthesized, for example, by the following method.

Wherein R ^p1 , n ^p1 and W ² have the same meanings as defined above.

The compound represented by the formula (M1-4-2c) can be produced, for example, by coupling reaction between a compound represented by the formula (M1-4-2a) and a compound represented by the formula (M1-4-2b) . This coupling reaction is the same as described for the compound represented by the formula (M1-1).

The compound represented by the formula (M1-4-2) can be prepared by, for example, reacting a compound represented by the formula (M1-4-2c) and a compound represented by the formula (M1-4-2d) - Miyaura - Hartwig reaction. &Lt; / RTI &gt;

The compound represented by the formula (M1-3) can be produced, for example, by coupling reaction between a compound represented by the formula (M1-5) and a compound represented by the formula (M1-6). This coupling reaction is the same as described for the compound represented by the formula (M1-1).

[Wherein,

E ¹ to E ⁴ , R ⁵ to R ¹⁰ , R ^1a to R ^4a , X ^a and X ^b have the same meanings as defined above.

W ³ and W ⁴ each independently represent a group represented by -B (OR ¹ ) ₂ , an alkylsulfonyloxy group, a cycloalkylsulfonyloxy group, an arylsulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom, The group may have a substituent.]

[Manufacturing Method 2]

The metal complex represented by the formula (1), which is a metal complex of the present invention, can also be produced by, for example, a method of reacting a precursor of a metal complex with a precursor of a ligand of a metal complex.

The metal complex represented by the formula (1) is, for example,

Can be produced by subjecting a compound represented by the formula (M1-4) to a coupling reaction with a metal complex represented by the formula (M1-7). This coupling reaction is the same as described for the compound represented by the formula (M1-1).

Wherein R ⁵ to R ¹⁰ , R ^1a to R ^4a , E ¹ to E ⁴ , n ₁ , n ₂ , X ^a , X ^b and A ¹ -G ¹ -A ² have the same meanings as defined above. ]

The metal complex represented by the formula (M1-7) can be obtained, for example, in the process A1 and the process B1 of the metal complex represented by the formula (1) Can be synthesized by using the compound represented by the formula (M1-3) instead of the compound represented by the formula (M1-3).

&Lt; Process for producing metal complex represented by formula (2)

[Manufacturing Method 3]

The metal complex represented by the formula (2) which is the metal complex of the present invention can be produced, for example, by the same method as the [production method 1] of the metal complex represented by the formula (1).

Specifically, by using a compound represented by the formula (M2-1) in place of the compound represented by the formula (M1-1) in the [production process 1] of the metal complex represented by the formula (1) A step A2 of synthesizing a metal complex represented by the formula (M2-2)

A step B2 of reacting a metal complex represented by the formula (M2-2) with a compound represented by the formula (M2-1) or a precursor of a ligand represented by A ¹ -G ¹ -A ² can do. Step A2 and Step B2 can be carried out in the same manner as Step A1 and Step B1 in [Production Method 1] of the metal complex represented by the above formula (1).

[Wherein E ¹ to E ⁴ , R ⁵ to R ¹⁴ , Y ^a and Y ^b have the same meanings as defined above]

Of the compounds represented by the formula (M2-1), when at least one selected from the group consisting of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a group represented by the formula (DA) or (DB) Can be synthesized by using a compound represented by the formula (M2-3) in place of the compound represented by the formula (M1-3) in the [Manufacturing Method 1] of the metal complex represented by the formula (1) have.

[Wherein E ¹ to E ⁴ , R ⁵ to R ¹⁰ , R ^1a to R ^4a , Y ^a , Y ^b , Z ¹ and W ¹ have the same meanings as defined above]

The compound represented by the formula (M2-3) can be obtained by using the compound represented by the formula (1) instead of the compound represented by the formula (M1-5) in the [production process 1] M2-5). &Lt; / RTI &gt;

[Wherein E ¹ to E ⁴ , R ⁵ to R ¹⁰ , R ^1a to R ^4a , Y ^a , Y ^b , W ³ and W ⁴ have the same meanings as defined above]

[Manufacturing Method 4]

The metal complex represented by the formula (2), which is the metal complex of the present invention, can be produced, for example, by the same method as the [production method 2] of the metal complex represented by the formula (1).

Specifically, by using a compound represented by the formula (M2-7) in place of the compound represented by the formula (M1-7) in the [production process 2] of the metal complex represented by the formula (1) Can be manufactured. This reaction can be carried out in the same manner as in the [production method 2] of the metal complex represented by the above formula (1).

Wherein R ⁵ to R ¹⁰ , R ^1a to R ^4a , E ¹ to E ⁴ , n ₁ , n ₂ , Y ^a , Y ^b and A ¹ -G ¹ -A ² have the same meanings as defined above. ]

[Coupling reaction in Production Method 1, Production Method 2, Production Method 3 and Production Method 4]

In the coupling reaction, a catalyst such as a palladium catalyst can be used to promote the reaction. Examples of the palladium catalyst include palladium acetate, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), [1,1'-bis (diphenylphosphino) Ferrocene] dichloropalladium (II), and tris (dibenzylideneacetone) 2-palladium (0).

Palladium catalysts include phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine and 1,1'-bis (diphenylphosphino) Can be used together.

When the palladium catalyst is used in the coupling reaction, the amount of the palladium catalyst may be, for example, the formula (M1-3), the formula (M1-4), the formula (M1-5) 3), Formula (M2-5) or Formula (M2-7), preferably 0.00001 to 10 moles in terms of palladium element.

In the coupling reaction, a base can be used in combination if necessary.

The compounds, catalysts and solvents used in the respective reactions described in &quot; Method for producing metal complexes &quot; may be used singly or in combination of two or more kinds.

&Lt; Metal-containing polymer compound &

(Hereinafter also referred to as &quot; metal-containing polymer &quot;) containing a structural unit having a group derived from the metal complex represented by the above formula (1) or (2) Has the same effect as the metal complex of the present invention.

Examples of the metal-containing structural unit include an arylene group or a divalent heterocyclic group having, as a substituent, a group obtained by removing one hydrogen atom from the metal complex represented by the above formula (1) or (2) A group obtained by removing one hydrogen atom from a metal complex represented by the formula (1) or (2), a group obtained by removing two hydrogen atoms from a metal complex represented by the formula (1) or (2) And a group in which three hydrogen atoms have been removed from the metal complex.

When the metal-containing polymer compound contains a group in which a hydrogen atom has been removed from the metal complex represented by the formula (1) or (2) as a constituent unit, the constituent unit is usually a constituent unit at the terminal. In the case where the metal-containing polymer compound includes a group in which a hydrogen atom has been removed from the metal complex represented by the formula (1) or (2) as a metal-containing structural unit, the metal- The branch is branching.

Examples of the metal-containing structural unit include structural units represented by the following formulas (3a) to (3h), and since the synthesis of the metal-containing polymer compound is easy, the structural units represented by formulas (3b), (3f) or (3h) is more preferable, and a structural unit represented by the formula (3c), (3f) or (3h) is more preferable and a structural unit represented by the formula (3f) Is more preferable.

[Wherein,

M, E ¹ , E ² , E ³ , E ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and A ¹ -G ¹ -A ² have the same meanings as defined above. When E ¹ is a nitrogen atom, R ²¹ does not exist, and when E ² is a nitrogen atom, R ²² does not exist, and when E ³ is a nitrogen atom, R ²³ does not exist and E ⁴ When it is a nitrogen atom, R &lt; ²⁴ &gt; does not exist.

n ₁ 'represents 0, 1 or 2; n ₂ 'represents 0, 1 or 2; When M is an iridium atom, n ₁ '+ n ₂ ' is 2, and when M is a platinum atom, n ₁ '+ n ₂ ' is 1.

n ₃ represents 2 or 3; When M is an iridium atom, n ₃ is 3, and when M is a platinum atom, n ₃ is 2.

n ₄ represents 0 or 1; n ₅ represents 0 or 1; When M is an iridium atom, n ₄ + n ₅ is 1, and when M is a platinum atom, n ₄ + n ₅ is 0.

R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom, May have substituents. When a plurality of R ²¹ , R ²² , R ²³ and R ²⁴ are present, they may be the same or different. R ²¹ and R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , and R ²⁴ and R ⁵ may combine with each other to form a ring together with the atoms to which they are bonded.

Z ^a and Z ^b each independently represent a direct bond, an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Za R ^Zb -, -CR ^Zc ₂ - or -NR ^Zc -. R ^Za represents an alkyl group or a cycloalkyl group, and these groups may have an aryl group or a monovalent heterocyclic group as a substituent. R ^Zb represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. R ^Zc represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of R ^Zc , they may be the same or different and may combine with each other to form a ring together with the carbon atoms to which they are attached. When ^a plurality of Z ^a and Z ^b are present, they may be the same or different. Provided that at least one of Z ^a and Z ^b is an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Za R ^Zb- , -CR ^Zc ₂ - or -NR ^Zc -.

Provided that at least one selected from the group consisting of R ²¹ , R ²² , R ²³ and R ²⁴ is a group represented by the formula (DA) or (DB), or at least one of Z ^a and Z ^b is -CR ^Za R ^Zb - Im.

W represents a group represented by the following formula (W1), (W2) or (W3).

nL represents an integer between 0 and 5 inclusive.

L represents an alkylene group, a cycloalkylene group, an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When there are plural L, they may be the same or different.

In formula (3a), E ¹ , E ² , E ³ or E ⁴ is bonded to L. In the formula (3b), the carbon atom bonding with R ⁶ , R ⁷ , R ⁸ or R ⁹ is bonded to L. In formula (3c), E ¹ , E ² , E ³ or E ⁴ is bonded to another structural unit, and the carbon atom bonded to R ⁶ , R ⁷ , R ⁸ or R ⁹ is bonded to another structural unit. In the formula (3d), E ¹ , E ² , E ³ or E ⁴ bond with other constituent units. In the formula (3e), the carbon atom bonded to R ⁶ , R ⁷ , R ⁸ or R ⁹ is bonded to another constituent unit. In the formula (3f), the carbon atom bonded to R ⁶ , R ⁷ , R ⁸ or R ⁹ is bonded to another constituent unit. In the formula (3g), E ¹ , E ² , E ³ or E ⁴ is bonded to another constituent unit. In the formula (3h), the carbon atom bonded to R ⁶ , R ⁷ , R ⁸ or R ⁹ is bonded to another constituent unit. When E ¹ and L or other constituent units are bonded, R ²¹ is not present. When E ² and L or other constituent units are bonded, R ²² is absent. When E ³ and L or other constituent units are bonded, R ²³ is not present. When E ⁴ and L or other constituent units are combined, R ²⁴ is absent. When a carbon atom and L or other structural units bonded in combination with R ^6, R ⁶ is not present. When a carbon atom and L or other structural units bonded in combination with R ^7, R ⁷ is not present. When a carbon atom and L or other structural units bonded in combination with R ^8, R ⁸ is not present. When a carbon atom and L or other structural units in combination with R ⁹ bond, R ⁹ is not present.]

[Wherein,

* Represents the binding hand with L.

Ar represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.

R ^W represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent. Plural R ^{W 's} may be the same or different and may be bonded to each other to form a ring together with the atoms to which they are bonded.]

In the formulas (3a) to (3e), when M is an iridium atom, n ₁ 'is preferably 1 or 2, more preferably 2, since the luminescent element using the metal-containing polymer compound is excellent in the lifetime . In the case where M is a platinum atom, n ₁ 'is preferably 1 since the luminescent device using the metal-containing polymer compound is excellent in luminance lifetime.

In the formula (3g) and the formula (3h), when M is an iridium atom, n ₄ is preferably 1 since the luminous means using the metal-containing polymer compound is excellent in lifetime.

At least one of the groups selected from the group consisting of R ²¹ , R ²² , R ²³ and R ²⁴ in formulas (3a) to (3h) is more excellent in the quantum yield of the metal-containing polymer compound, ).

In the formulas (3a) to (3h), R a ^21, R ^22, R ²³ and R ²⁴ are if multiple presence each of the plurality present all of R ²¹ all, a plurality existence R ²² in which, for a plurality existence R ²³ Or all of R ²⁴ present in all or a plurality of groups is a group represented by formula (DA) or (DB).

Among the formulas (3a) to (3h), at least one selected from the group consisting of R ²¹ , R ²² , R ²³ and R ²⁴ is more excellent in the quantum yield of the metal-containing polymeric compound, , More preferably a group represented by the formula (D-A1), (D-A2) or (D-A3) and still more preferably a group represented by the formula (D-A3).

Among the formulas (3a) to (3h), R ²² is preferably a group represented by the formula (DA) or (DB) and is preferably a group represented by the formula (DA) since the quantum yield of the metal- , More preferably a group represented by the formula (D-A1), (D-A2) or (D-A3), particularly preferably a group represented by the formula (D-A3).

In the formulas (3a) to ^{(3h), R 21, R} 22, R 23 and R, if ²⁴ is a group other than the group represented by formula (DA), or ^{(DB), R 21, R} 22, R 23 and R ²⁴ Is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, because the synthesis of the metal- More preferably a hydrogen atom.

Equation (3a) to (3h) of, Z is ^a direct bond, an oxygen atom, a sulfur atom, -CR R ^{Za Zb} -, -CR ^Zc ₂ - or -NR ^Zc - it is not preferred, and a direct bond, -CR ^Za R ^Zb - or -CR ^Zc ₂ -, more preferably -CR ^Za R ^Zb- or -CR ^Zc ₂ -, and particularly preferably -CR ^Za R ^Zb -.

Formula (3a) to (3h) of, Z ^b is a direct bond, an oxygen atom, a sulfur atom, -CR R ^{Za Zb} -, -CR ^Zc ₂ - or -NR ^Zc - is not preferred, and a direct bond, -CR ^Za More preferably R ^Zb - or -CR ^Zc ₂ -, more preferably a direct bond or -CR ^Za R ^Zb -, particularly preferably a direct bond.

Provided that at least one of Z ^a and Z ^b is an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Za R ^Zb- , -CR ^Zc ₂ - or -NR ^Zc -.

Among the formulas (3a) to (3h), the combination of Z ^a and Z ^b is more preferable because the quantum yield of the metal-containing polymer compound is better,

A combination wherein Z ^a is -CR ^Za R ^Zb - and Z ^b is a direct bond, a combination wherein Z ^a is -CR ^Za R ^Zb - and Z ^b is -NR ^Zc -, Z ^a is -CR ^Za R ^Zb - and Z ^b A combination wherein Z ^a is -CR ^Za R ^Zb - and Z ^b is a sulfur atom, a combination wherein Z ^a is a direct bond and Z ^b is -CR ^Za R ^Zb -, Z ^a is -NR ^Zc - Z is -CR ^b R ^{Za Zb} - combination, Z ^a is an oxygen atom and Z is -CR ^b R ^{Za Zb} - combination, Z is ^a sulfur atom and Z is -CR ^b R ^{Za Zb} - combination, ^a Z ^Zc is -CR ₂ -, and Z ^b is a direct bond in combination, ^a Z ^Zc -CR ₂ - and Z is -NR ^{b Zc} - is a combination, the Z ^a is an oxygen atom and Z ^b is a direct bond combination, ^a Z and Z ^b is a direct bond combination, Z ^a - is an oxygen atom and Z is -NR ^{b Zc} - combination, Z is ^a sulfur atom and Z ^b is a direct bond combination, Z is ^a -C (= O) -NR ^Zc - is a direct bond and Z ^b in combination, Z is ^a direct bond and Z ^b is -CR ₂ ^Zc - is a combination, or Z is ^a direct bond and Z ^b is a combination of a sulfur atom wind Directly,

Z is -CR ^a R ^{Za Zb} - and Z ^b is a direct bond combination, Z is ^a direct bond and Z is -CR ^b R ^{Za Zb} - combination, Z is ^a -CR ^Zc ₂ -, and Z ^b is a direct bond Or ^a combination wherein Z ^a is a direct bond and Z ^b is -CR ^Zc ₂ - is more preferable,

Z is -CR ^a R ^{Za Zb} - and Z ^b is a direct bond in combination, or Z is ^a -CR ^Zc ₂ -, and Z ^b is a direct bond, and more preferably in combination,

Particularly preferred is a combination wherein Z ^a is -CR ^Za R ^Zb - and Z ^b is a direct bond.

Among the formulas (3a) to (3h), R ^Za is preferably an alkyl group which may have a substituent since the luminous means using the metal-containing polymer compound is excellent in the lifetime.

Among the formulas (3a) to (3h), R ^Zb is preferably an aryl group which may have a substituent, and is preferably a phenyl group which may have a substituent, because the lifetime of the light-emitting device using the metal- desirable.

Of the formulas (3a) to (3h), R ^Zc is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group because the luminescent device using the metal-containing polymer compound is excellent in the lifetime. More preferable.

Among the formulas (3a) and (3b), W is preferably a group represented by the formula (W1) since the external quantum efficiency of the light emitting device using the metal-containing polymer compound is excellent.

Of the formulas (3a) and (3b), nL is preferably an integer of 0 to 2, more preferably 0 or 1. Among the formulas (3a) and (3b), L is preferably an alkylene group or an arylene group, and more preferably an arylene group.

In the formula (W1), Ar is preferably an aromatic hydrocarbon group.

Of the formulas (W2) and (W3), RW is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

Examples of the metal-containing structural units include structural units represented by the following formulas (Ir-301) to (Ir-310).

In the metal-containing polymer compound, the metal-containing structural units may be contained singly or in combination of two or more.

The metal-containing polymer compound preferably contains a constituent unit other than the metal-containing constituent unit. The constituent unit other than the metal-containing constituent unit is preferably at least one constituent unit selected from the group consisting of a constituent unit represented by the following formula (Y) and a constituent unit represented by the following formula (X).

In the metal-containing polymer compound, the content of the metal-containing structural unit is preferably 0.1 to 30 parts by weight based on the total amount of the structural units contained in the metal-containing polymer compound, since the external quantum efficiency of the light- Mol%, more preferably 0.5 to 15 mol%, and still more preferably 1 to 8 mol%.

The metal-containing polymer compound can be produced, for example, by the same method as the < method for producing a polymer host &quot; described below, using a compound represented by the following formula (4).

[Wherein,

MR represents a metal-containing constituent unit.

nV represents 1, 2 or 3;

V represents a group selected from Substituent Group A, or a group selected from Substituent Group B; When there are plural V, they may be the same or different.]

<Substituent group A>

A group represented by a chlorine atom, a bromine atom, an iodine atom, -OS (= O) ₂ R ^{C1 wherein} R ^C1 represents an alkyl group, a cycloalkyl group or an aryl group and these groups may have a substituent.

<Substituent Group B>

-B of (OR ^C2) ₂ (formula, R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may be have a substituent. R presence plurality ^C2 may be the same or different to, connected to each other And each may form a cyclic structure together with the oxygen atom to which they are attached;

-BF ₃ Q 'wherein Q' represents Li, Na, K, Rb or Cs;

-MgY '(wherein Y' represents a chlorine atom, a bromine atom or an iodine atom);

-ZnY "(wherein Y" represents a chlorine atom, a bromine atom or an iodine atom); And

-Sn (R ^C3 ) ₃ (wherein R ^C3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent. The plurality of R ^C3 may be the same or different, , Each of which may form a cyclic structure together with the tin atom to which it is bonded.

As the group represented by -B (OR ^C2 ) ₂ , a group represented by the following formula is exemplified.

<Composition>

The composition of the present invention can be used in combination with at least one kind of material selected from the group consisting of a hole transporting material, a hole injecting material, an electron transporting material, an electron injecting material, a light emitting material (different from the metal complex of the present invention) , And a metal complex of the present invention.

In the composition of the present invention, the metal complex of the present invention may be contained singly or in combination of two or more.

[Host material]

The metal complex of the present invention can be formed into a composition with a host material having at least one function selected from the group consisting of hole injecting property, hole transporting property, electron injecting property and electron transporting property, whereby the external quantum of the light emitting device obtained using the metal complex of the present invention The efficiency becomes better. In the composition of the present invention, the host material may be contained singly or in combination of two or more.

In the metal complex of the present invention and the composition containing the host material, the content of the metal complex of the present invention is usually from 0.01 to 80 parts by weight, preferably from 0.01 to 80 parts by weight, based on 100 parts by weight of the total of the metal complex and the host material of the present invention Is preferably 0.05 to 40 parts by weight, more preferably 0.1 to 20 parts by weight, and still more preferably 1 to 20 parts by weight.

The minimum excitation triplet state (T ₁ ) of the host material is superior to that of the light emitting device obtained using the composition of the present invention, so that the minimum excitation triplet state (T ₁ ) of the metal complex of the present invention and An equivalent energy level, or a higher energy level.

As the host material, it is preferable that the host material exhibits solubility in a solvent capable of dissolving the metal complex of the present invention, from the viewpoint of producing the light emitting element obtained by using the composition of the present invention in a solution coating process.

Host materials are classified as low molecular compounds and high molecular compounds.

Examples of the low-molecular compound used in the host material include compounds having a carbazole skeleton, compounds having a trilaurylamine skeleton, compounds having a phenanthroline skeleton, compounds having a triaryltriazine skeleton, compounds having an azole skeleton, A compound having a benzothiophene skeleton, a compound having a benzofuran skeleton, a compound having a fluorene skeleton, and a compound having a spirofluorene skeleton. Examples of the low-molecular compound used in the host material include the compounds represented by the following.

The polymer compound used for the host material includes, for example, a polymer compound which is a hole transporting material to be described later, and a polymer compound which is an electron transporting material described later.

[Polymer host]

(Hereinafter also referred to as &quot; polymer host &quot;) preferable as a host compound will be described.

As the polymer host, a polymer compound containing a constituent unit represented by the formula (Y) is preferable.

[ ^Wherein Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these groups may have a substituent]

The arylene group represented by Ar ^Y1 is more preferably an arylene group represented by the formula (A-1), the formula (A-2), the formula (A-6) to the formula (A- A-20), more preferably a group represented by the formula (A-1), the formula (A-2), the formula (A-7), the formula (A- And these groups may have a substituent.

The divalent heterocyclic group represented by Ar ^Y1 is more preferably a group represented by the formula (AA-1) to (AA-4), the formula (AA-10) to the formula (AA- (AA-4), (AA-10), (AA-12) and (AA-34) , A group represented by the formula (AA-14) or (AA-33), and these groups may have a substituent.

The more preferable range and the more preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group represented by Ar ^Y1 and the at least one divalent heterocyclic group are directly bonded are A more preferable range of the arylene group and a divalent heterocyclic group represented by Ar ^Y1 , and a more preferable range thereof.

The "bivalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded" includes, for example, groups represented by the following formulas, and they may have a substituent.

[Wherein R ^XX represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent]

R ^XX is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.

The substituent which the group represented by Ar ^Y1 may have is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may also have a substituent.

Examples of the structural unit represented by the formula (Y) include structural units represented by the formulas (Y-1) to (Y-10) (Y-1), (Y-2) or (Y-3) from the viewpoint of the luminance lifetime of the compound Y-7), and is preferably a structural unit represented by the formula (Y-8) to (Y-10) from the viewpoint of hole transportability.

[Wherein R ^Y1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. Plural R ^{Y1 s} may be the same or different and adjacent R ^{Y1 s} may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.

R ^Y1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.

^Wherein R ^Y1 has the same meaning as defined above. X ^Y1 represents a group represented by -C (R ^Y2 ) ₂ -, -C (R ^Y2 ) = C (R ^Y2 ) - or C (R ^Y2 ) ₂ -C (R ^Y2 ) ₂ -. R ^Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. The plural R ^{Y2 s} may be the same or different and R ^{Y2 s} may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.

R ^Y2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.

The combination of two R ^Y2 groups in the group represented by -C (R ^Y2 ) ₂ - in X ^Y1 is preferably an alkyl group or a cycloalkyl group on both sides, an aryl group on both sides, a monovalent heterocyclic group on both sides, An alkyl group or a cycloalkyl group, and the other is an aryl group or a monovalent heterocyclic group, more preferably one is an alkyl group or a cycloalkyl group and the other is an aryl group, and these groups may have a substituent. The two R ^Y2 present may combine with each other to form a ring together with the atoms to which they are bonded, and when R ^Y2 forms a ring, the group represented by -C (R ^Y2 ) ₂ - is preferably Is a group represented by the formula (Y-A1) to (Y-A5), more preferably a group represented by the formula (Y-A4), and these groups may have a substituent.

In X ^Y1 , the combination of two R ^Y2 groups in the group represented by -C (R ^Y2 ) = C (R ^Y2 ) - is preferably an alkyl group or a cycloalkyl group, or an alkyl group or a cycloalkyl group, Is an aryl group, and these groups may have a substituent.

In X ^Y1 , four R ^Y2 in the group represented by -C (R ^Y2 ) ₂ -C (R ^Y2 ) ₂ - are preferably an alkyl group or a cycloalkyl group which may have a substituent. A plurality of R ^Y2 may be bonded to each other to form a ring together with the atoms to which they are bonded, and when R ^Y2 forms a ring, it may be represented by -C (R ^Y2 ) ₂ -C (R ^Y2 ) ₂ - Is preferably a group represented by the formula (Y-B1) to (Y-B5), more preferably a group represented by the formula (Y-B3), and these groups may have a substituent.

[ ^Wherein R ^Y2 has the same meaning as defined above]

^Wherein R ^Y1 has the same meaning as defined above. R ^Y3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.

R ^Y3 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups may have a substituent.

^Wherein R ^Y1 has the same meaning as defined above. R ^Y4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.

R ^Y4 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups may have a substituent.

Examples of the structural unit represented by the formula (Y) include structural units containing an arylene group represented by the formulas (Y-101) to (Y-121), structural units represented by the formulas (Y-201) A structural unit comprising a divalent heterocyclic group to be represented, a divalent group in which at least one arylene group represented by formulas (Y-301) to (Y-304) and at least one divalent heterocyclic group are directly bonded to each other And a structural unit.

The constitutional unit represented by the formula (Y) wherein Ar ^Y1 is an arylene group is excellent in the lifetime of the light emitting device using the composition of the polymeric host and the metal complex of the present invention, so that the total amount of the constituent units , Preferably 0.5 to 100 mol%, and more preferably 60 to 95 mol%.

A structural unit represented by the formula (Y) wherein Ar ^Y1 is a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, Is preferably 0.5 to 30 mol%, and more preferably 3 to 20 mol%, based on the total amount of the constituent units contained in the polymer compound, because the charge transportability of the light emitting device using the composition of the metal complex is excellent.

The structural unit represented by the formula (Y) may contain only one type or two or more types in the polymer host.

Since the polymer host has excellent hole transportability, it is preferable to further include a structural unit represented by the following formula (X).

^Wherein a ^X1 and a ^X2 each independently represent an integer of 0 or more. Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these groups may have a substituent . R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.

a ^X1 is preferably not more than 2, more preferably not more than 1, because the lifetime of the light emitting device using the composition of the polymer host and the metal complex of the present invention is excellent.

a ^X2 is preferably 2 or less, and more preferably 0 because the lifetime of the light emitting device using the composition of the polymeric host and the metal complex of the present invention is excellent.

R ^X1 , R ^X2 and R ^X3 are preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups may have a substituent.

The arylene group represented by Ar ^X1 and Ar ^X3 is more preferably a group represented by the formula (A-1) or (A-9), more preferably a group represented by the formula (A-1) , These groups may have substituents.

The divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 is more preferably a group represented by formula (AA-1), formula (AA-2) or formula (AA-7) to formula (AA-26) , These groups may have substituents.

Ar ^X1 and Ar ^X3 are preferably an arylene group which may have a substituent.

The arylene group represented by Ar ^X2 and Ar ^X4 is more preferably an arylene group represented by the formula (A-1), the formula (A-6), the formula (A-7), the formula (A- Or a group represented by the formula (A-19), and these groups may have a substituent.

The more preferable range of the divalent heterocyclic group represented by Ar ^X2 and Ar ^X4 is the same as the more preferable range of the divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 .

The more preferable range and more preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 are directly bonded to at least one divalent heterocyclic group are , The arylene group represented by Ar ^X1 and Ar ^X3 , and the divalent heterocyclic group, and more preferably the same.

As the divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 is directly bonded to at least one divalent heterocyclic group, at least one arylene group represented by Ar ^Y1 of the formula (Y) And the divalent heterocyclic group of the species is the same as the divalent group directly bonded thereto.

Ar ^X2 and Ar ^X4 are preferably an arylene group which may have a substituent.

The substituent which the group represented by Ar ^X1 to Ar ^X4 and R ^X1 to R ^X3 may have is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may further have a substituent.

The structural unit represented by the formula (X) is preferably a structural unit represented by the formula (X-1) to (X-7), more preferably a structural unit represented by the formula (X-1) (X-3) to (X-6), and more preferably a structural unit represented by the formula (X-3) to (X-6).

R ^X4 and R ^X5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group or a cyano group, The group may have a substituent. Multiple R ^x4s may be the same or different. Plural R ^X5s may be the same or different and adjacent R ^X5 may be bonded to each other to form a ring together with the carbon atoms to which they are attached.

The constituent unit represented by the formula (X) is preferably 0.1 to 50 mol%, more preferably 1 to 40 mol% based on the total amount of the constituent units contained in the polymer host, And preferably 2 to 30 mol%.

Examples of the structural unit represented by the formula (X) include a structural unit represented by the formula (X1-1) to (X1-11), preferably a structural unit represented by the formula (X1-3) to (X1-10 ).

In the polymer host, the structural unit represented by the formula (X) may be contained in only one kind or may contain two or more kinds.

Examples of the polymer host include the polymer compounds P-1 to P-7 shown in Table 1 below. Here, the "other" structural unit means a structural unit other than the structural unit represented by formula (Y) and the structural unit represented by formula (X).

[In the table, p, q, r, s and t represent molar ratios of the constituent units. p + q + r + s + t = 100, and 100? p + q + r + s? 70. The other structural unit means a structural unit other than the structural unit represented by the formula (Y) and the structural unit represented by the formula (X).

The polymer host may be any of a block copolymer, a random copolymer, an alternate copolymer and a graft copolymer, and may be in any other form, but is preferably a copolymer formed by copolymerizing a plurality of raw material monomers.

&Lt; Preparation method of polymer host >

The polymeric host can be prepared by a known polymerization method as described in Chemical Review (Chem. Rev.), Vol. 109, p. 897-1091 (2009), for example Suzuki reaction, Yamamoto reaction, Buchwald ), A Stille reaction, a Negishi reaction, and a Kumada reaction. The reaction may be carried out by a coupling reaction using a transition metal catalyst.

In the above polymerization method, the monomer may be introduced by a method in which all of the monomers are added all at once into the reaction system, a method in which a part of the monomers is added and reacted, and the remaining monomers are charged, Or a method of dividing and injecting them.

Examples of the transition metal catalyst include a palladium catalyst and a nickel catalyst.

The post-treatment of the polymerization reaction may be carried out by a known method, for example, a method of removing water-soluble impurities by separating liquid, a method of adding a reaction solution after polymerization to a lower alcohol such as methanol, filtering the precipitated precipitate, Alone or in combination. When the purity of the polymer host is low, it can be purified by a conventional method such as recrystallization, reprecipitation, continuous extraction by a Soxhlet extractor, column chromatography and the like.

The metal complex of the present invention and a composition containing a solvent (hereinafter sometimes referred to as &quot; ink &quot;) are suitable for the production of a light emitting device using a printing method such as an inkjet printing method or a nozzle printing method.

The viscosity of the ink may be adjusted according to the type of the printing method. In the case where the solution such as the ink jet printing method is applied to the printing method via the discharging device, the viscosity is preferably 25 Lt; 0 &gt; C.

The solvent contained in the ink is preferably a solvent capable of dissolving or uniformly dispersing the solid content in the ink. Examples of the solvent include chlorinated solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; Ether solvents such as tetrahydrofuran, dioxane, anisole, and 4-methyl anisole; Aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, ethylbenzene, n-hexylbenzene, and cyclohexylbenzene; Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane and bicyclohexyl; Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and acetophenone; Ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate; Polyhydric alcohol solvents such as ethylene glycol, glycerin, and 1,2-hexanediol; Alcohol solvents such as isopropyl alcohol and cyclohexanol; Sulfoxide-based solvents such as dimethylsulfoxide; Amide solvents such as N-methyl 2-pyrrolidone and N, N-dimethylformamide. The solvent may be used alone, or two or more solvents may be used in combination.

In the ink, the blending amount of the solvent is usually 1000 to 100000 parts by weight, preferably 2000 to 20000 parts by weight, per 100 parts by weight of the metal complex of the present invention.

[Hole transport material]

The hole transporting material is classified into a low molecular compound and a high molecular compound, and a polymer compound is preferable, and a polymer compound having a crosslinking group is more preferable.

Examples of the polymer compound include polyvinylcarbazole and derivatives thereof; And polyarylenes and derivatives thereof having an aromatic amine structure in the side chain or main chain. The polymer compound may be a compound having an electron-accepting moiety bonded thereto. Examples of the electron-accepting moiety include fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone, and the like, preferably fullerene.

In the composition of the present invention, the compounding amount of the hole transporting material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight, per 100 parts by weight of the metal complex of the present invention.

The hole transporting material may be used alone or in combination of two or more.

[Electronic transport material]

Electron transport materials are classified as low molecular compounds and high molecular compounds. The electron transporting material may have a crosslinking group.

Examples of the low-molecular compound include a metal complex having 8-hydroxyquinoline as a ligand, a metal complex such as oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, di Phenyldicyanoethylene, diphenoquinone, and derivatives thereof.

Examples of the polymer compound include polyphenylene, polyfluorene, and derivatives thereof. The polymer compound may be doped with a metal.

In the composition of the present invention, the blending amount of the electron transporting material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight, per 100 parts by weight of the metal complex of the present invention.

The electron transporting materials may be used alone or in combination of two or more.

[Hole injection material and electron injection material]

The hole injecting material and the electron injecting material are classified into a low molecular compound and a high molecular compound, respectively. The hole injecting material and the electron injecting material may have a crosslinking group.

Examples of the low-molecular compound include metal phthalocyanines such as copper phthalocyanine; Carbon; Metal oxides such as molybdenum and tungsten; And metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride, and potassium fluoride.

Examples of the polymer compound include polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinoline and polyquinoxaline, and derivatives thereof; A conductive polymer such as a polymer containing a group represented by the formula (X) in the main chain or side chain.

In the composition of the present invention, the blending amounts of the hole injecting material and the electron injecting material are usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the metal complex of the present invention.

Each of the hole injecting material and the electron injecting material may be used singly or in combination of two or more kinds.

[Ion doping]

When the hole injecting material or the electron injecting material comprises a conductive polymer, the electrical conductivity of the conductive polymer is preferably 1 x 10 ^-5 S / cm to 1 x 10 ³ S / cm. In order to set the electric conductivity of the conductive polymer to such a range, an appropriate amount of ions can be doped to the conductive polymer.

The kind of ions to be doped is anion if it is a hole injection material, and cation if it is an electron injection material. Examples of the anion include a polystyrenesulfonic acid ion, an alkylbenzenesulfonic acid ion, and a camphorsulfonic acid ion. Examples of the cation include lithium ion, sodium ion, potassium ion and tetrabutylammonium ion.

The doping ions may be one species or more than two species.

[Light Emitting Material]

The light emitting material (different from the metal complex of the present invention) is classified into a low molecular compound and a high molecular compound. The light emitting material may have a crosslinking group.

Examples of the low-molecular compound include naphthalene and derivatives thereof, anthracene and derivatives thereof, perylene and derivatives thereof, and triplet light-emitting complexes comprising iridium, platinum or europium as a central metal.

Examples of the polymer compound include a phenylene group, a naphthalenediyl group, a fluorenediyl group, a phenanthrenyl group, a dihydrophenanthrenediyl group, a group represented by the formula (X), a carbazolyldiol group, Anthracenediyl group, pyridinyl group, and the like.

The light emitting material includes a low molecular weight compound and a high molecular weight compound, or preferably includes a triplet light emitting complex and a high molecular weight compound.

Examples of the triplet light-emitting complex include metal complexes shown below.

In the composition of the present invention, the content of the light emitting material is usually 0.1 to 400 parts by weight based on 100 parts by weight of the metal complex of the present invention.

[Antioxidant]

The antioxidant may be any compound which is soluble in the same solvent as the metal complex of the present invention and does not inhibit luminescence and charge transport, and examples thereof include phenolic antioxidants and phosphorus antioxidants.

In the composition of the present invention, the blending amount of the antioxidant is usually 0.001 to 10 parts by weight based on 100 parts by weight of the metal complex of the present invention.

Antioxidants may be used alone or in combination of two or more.

<Act>

The film obtained by using the metal complex of the present invention is classified into a film containing the metal complex of the present invention and an insoluble film in which the metal complex of the present invention is insolubilized with respect to the solvent by crosslinking. The insoluble film is a film obtained by crosslinking the metal complex of the present invention by external stimulation such as heating or light irradiation. Since the insoluble film is substantially insoluble in a solvent, it can be suitably used for lamination of light emitting devices.

The heating temperature for crosslinking the film is usually 25 to 300 占 폚 and preferably 50 to 250 占 폚, and more preferably 150 to 200 占 폚 because the external quantum efficiency becomes good.

The kind of light used for light irradiation for crosslinking the film is, for example, ultraviolet light, near ultraviolet light, or visible light.

The film is suitable as the light emitting layer in the light emitting element.

The film can be formed by using the ink, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, A flexographic printing method, an offset printing method, an inkjet printing method, a capillary coating method, and a nozzle coating method.

The thickness of the film is usually 1 nm to 10 탆.

&Lt; Light emitting element &

The light emitting element of the present invention is a light emitting element obtained by using the metal complex of the present invention, and the metal complex of the present invention is cross-linked in the molecule or between molecules, or the metal complex of the present invention is cross- .

The light-emitting element structure of the present invention has, for example, an electrode including an anode and a cathode, and a layer obtained by using the metal complex of the present invention provided between the electrode and the electrode.

[Floor composition]

The layer obtained by using the metal complex of the present invention is usually at least one layer of a light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer, and an electron injecting layer, and is preferably a light emitting layer. These layers include a light emitting material, a hole transporting material, a hole injecting material, an electron transporting material, and an electron injecting material, respectively. These layers are formed by dissolving a light emitting material, a hole transporting material, a hole injecting material, an electron transporting material, and an electron injecting material in the above-described solvent to prepare an ink and using the same method as the above- can do.

The light emitting element has a light emitting layer between the anode and the cathode. The light emitting element of the present invention preferably has at least one layer of a hole injecting layer and a hole transporting layer between the anode and the light emitting layer from the viewpoints of hole injecting property and hole transporting property and in view of electron injecting property and electron transporting property, And at least one layer of an electron injecting layer and an electron transporting layer is preferably provided between the light emitting layer and the light emitting layer.

As the material of the hole transporting layer, electron transporting layer, light emitting layer, hole injecting layer and electron injecting layer, the hole transporting material, the electron transporting material, the light emitting material, the hole injecting material and the electron injecting material, .

The material of the hole transporting layer, the material of the electron transporting layer and the material of the light emitting layer, when they are dissolved in the solvent used in forming the layers adjacent to the hole transporting layer, the electron transporting layer and the light emitting layer, In order to prevent the material from dissolving, it is preferable that the material has a crosslinking group. It is possible to insolubilize the layer by forming each layer using a material having a crosslinking group and then crosslinking the crosslinking group.

In the light emitting device of the present invention, as a method of forming each layer such as a light emitting layer, a hole transporting layer, an electron transporting layer, a hole injecting layer, and an electron injecting layer, when a low molecular compound is used, for example, A method of forming a film from a molten state, and a method of forming a film from a solution or a molten state when a polymer compound is used.

The order, number and thickness of the layers to be laminated may be adjusted in consideration of external quantum efficiency and device lifetime.

[Substrate / Electrode]

The substrate in the light-emitting element is a substrate that can form an electrode and does not chemically change when forming an organic layer, and is a substrate including a material such as glass, plastic, or silicon. In the case of an opaque substrate, it is preferred that the furthest electrode from the substrate be transparent or translucent.

Examples of the material of the anode include a conductive metal oxide and a semitransparent metal, and preferably indium oxide, zinc oxide, tin oxide; Conductive compounds such as indium tin oxide (ITO), indium zinc oxide, and the like; A complex of silver and palladium and copper (APC); NESA, gold, platinum, silver and copper.

Examples of the material of the negative electrode include metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc and indium; At least two of them; At least one of them, and at least one of silver, copper, manganese, titanium, cobalt, nickel, tungsten, and tin; And graphite and graphite intercalation compounds. Examples of the alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys and calcium-aluminum alloys.

The positive electrode and the negative electrode may each have a laminated structure of two or more layers.

[Usage]

In order to obtain planar light emission by using the light emitting element, the planar anode and the cathode may be arranged so as to overlap with each other. In order to obtain luminescence on the pattern, a method of providing a patterned window mask on the surface of the light emitting element on the surface, a method of forming a non-luminescent portion to an extremely thick layer to make it substantially non-luminescent, There is a method of forming both electrodes in a pattern shape. A segment type display device capable of displaying numbers, characters, and the like can be obtained by forming a pattern by any of these methods and disposing a number of electrodes so that they can be independently turned ON / OFF. In order to form a dot matrix display device, both the positive electrode and the negative electrode may be formed in a stripe shape and arranged so as to be perpendicular to each other. A partial color display or a multicolor display can be realized by a method of applying a plurality of kinds of polymer compounds having different light emission colors in a divided manner and a method of using a color filter or a fluorescent conversion filter. The dot matrix display device can be passively driven, and can be actively driven in combination with a TFT or the like. These display devices can be used for displays such as computers, televisions, and mobile terminals. The light emitting element on the surface can be suitably used as a planar light source for a backlight of a liquid crystal display device or as a light source for illumination on a plane. If a flexible substrate is used, it can also be used as a curved light source and a display device.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

LC-MS was measured by the following method.

The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg / mL, and about 1 μL was injected into an LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). The mobile phase of the LC-MS was used while varying the ratio of acetonitrile and tetrahydrofuran, and flowed at a flow rate of 0.2 mL / min. The column used was L-column 2 ODS (3 탆) (manufactured by Chemical Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle diameter: 3 탆).

NMR was measured by the following method.

5 to 10 mg of the sample to be measured was dissolved in about 0.5 mL of a medium of chloroform (CDCl ₃ ), tetrahydrofuran (THF-d ₈ ) or methylene chloride (CD ₂ Cl ₂ ) , Inc., product name: MERCURY 300).

As an indicator of the purity of the compound, a value of high performance liquid chromatography (HPLC) area percentage was used. This value is a value at 254 nm in high performance liquid chromatography (HPLC, product name: LC-20A, Shimadzu Seisakusho Co., Ltd.) unless otherwise specified. At this time, the compound to be measured was dissolved in tetrahydrofuran or chloroform so as to have a concentration of 0.01 to 0.2% by weight, and 1 to 10 μL was injected into the HPLC according to the concentration. Acetonitrile and tetrahydrofuran were used for the mobile phase of HPLC, and eluted with a gradient analysis of acetonitrile / tetrahydrofuran = 100/0 to 0/100 (volume ratio) at a flow rate of 1 mL / min. The column used was Kaseisorb LC ODS 2000 (manufactured by Tokyo Kasei Kogyo Co.) or an ODS column having equivalent performance. A photodiode array detector (Shimadzu Seisakusho Co., Ltd., product name: SPD-M20A) was used as the detector.

TLC-MS was measured by the following method.

The measurement sample was dissolved in toluene, tetrahydrofuran or chloroform and applied on a TLC plate for DART (YSK5-100 manufactured by Techno Applications). TLC-MS (trade name JMS-T100TD manufactured by JEOL Ltd.) (The AccuTOF TLC)). The helium gas temperature during the measurement was adjusted in the range of 200 to 400 캜.

PLQY and emission spectrum were measured by the following methods.

The metal complex was dissolved in xylene to a concentration of 0.0008% by weight. The obtained xylene solution was placed in a quartz cell having a square of 1 cm on one side and then bubbled with nitrogen gas to prepare a measurement sample by degassing the oxygen. PLQY and luminescence spectrum were measured using an absolute PLGA quantum yield measuring apparatus (automatic control electric monochrome light source type) (C9920-02G, manufactured by Hamamatsu Photonics K.K.), and from the obtained luminescence spectrum, (Hereinafter also referred to as &quot; FWHM &quot;) of the spectrum was calculated. Specifically, FWHM is calculated from the wavelength at which the normalized light emission intensity is 0.5 when the light emission intensity of the maximum peak in the emission spectrum of the metal complex is normalized to 1.0. When three or more wavelengths having normalized light emission intensity of 0.5 exist, the wavelength is calculated at the shortest wavelength and the longest wavelength. The excitation wavelength was 380 nm.

Example 1 Synthesis of Metal Complex M1

(Stage 1: synthesis of compound L1c)

After the inside of the reaction vessel was set in an argon gas atmosphere, the compound L1a (12 g), the compound L1b (5.7 g), toluene 140 mL, tert-butanol 90 mL, tetrahydrofuran 70 mL, (Triphenylphosphine) palladium (0) (530 mg) and a 40 wt% aqueous solution of tetrabutylammonium hydroxide (60 g) were added and the mixture was stirred at 50 ° C for 15 hours.

After the obtained reaction mixture was cooled to room temperature, toluene was added and the obtained organic layer was washed with ion-exchanged water. Thereafter, the filtrate was dried with anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure to give an oil.

The resulting oil was purified by silica gel column chromatography (mixed solvent of toluene and hexane) and then dried under reduced pressure to obtain compound L1c (10 g, yield 80%) as a colorless oil. The HPLC area percentage value of the compound L1c was 99.5% or more.

TLC-MS (DART positive): m / z = 546 [M + H] &lt; ^{+ &}

(Stage 2: synthesis of compound L1e)

After the inside of the reaction vessel was put in an argon gas atmosphere, the compound L1c (10 g), the compound L1d (7.2 g), [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct PdCl ₂ (dppf) 揃 CH ₂ Cl ₂ , 780 mg), potassium acetate (5.6 g) and 1,2-dimethoxyethane (60 mL) were added and the mixture was stirred under reflux for 2 hours.

The resulting reaction mixture was cooled to room temperature, toluene (90 mL) was added, and the mixture was filtered through a Celite filter, and the filtrate was concentrated under reduced pressure. Thereafter, hexane and activated carbon were added thereto, and the mixture was stirred at 60 ° C for 1 hour, filtered through a filter with Celite, and the filtrate was concentrated under reduced pressure to obtain Compound L1e (12 g) as a colorless oil. The percentage HPLC area percentage of compound L1e was 99.0%.

(Stage 3: synthesis of compound L1)

The reaction vessel was shaded and the inside of the reaction vessel was put in an argon gas atmosphere and then the compound L1e (12 g), the compound L1f (8.7 g), tetrakis (triphenylphosphine) palladium (0) (440 mg), toluene % Tetraethylammonium hydroxide aqueous solution (56 g) was added, and the mixture was stirred at 70 占 폚 for 3 hours. Compound L1f was synthesized according to the method described in JP-A-2008-179617.

After the obtained reaction mixture was cooled to room temperature, toluene was added and the obtained organic layer was washed with ion-exchanged water. Then, it was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a solid.

This solid was purified by silica gel column chromatography (mixed solvent of toluene and hexane) and then dried under reduced pressure to obtain Compound LI (9.3 g, yield 60% for compound L1c) as a pale yellow solid. The HPLC area percentage value of the compound L1 was 99.5% or more.

TLC-MS (DART positive): m / z = 812 [M + H] &lt; ^{+ &}

_{^{1 H-NMR (CD 2 Cl}} 2, 300㎒): δ (ppm) = 10.02 (d, 1H), 9.07 (dd, 1H), 8.72 (dt, 4H), 8.23 (s, 1H), 8.19 (dd (M, 1H), 8.06 (d, 1H), 7.87 (d, 1H), 7.81-7.78 ), 1.43 (s, 18H), 1.21-1.07 (m, 20H), 0.80 (t, 6H), 0.75-0.56 (m, 4H).

(Stage 4: synthesis of metal complex M1a)

After the inside of the shaking reaction vessel was set to an argon gas atmosphere, Compound L 1 (480 mg) and 2-ethoxyethanol (40 mL) were added and heated to 60 ° C. Thereafter, a hydrate of iridium (III) chloride (88 mg) dissolved in ion-exchanged water (13 mL) was added thereto, followed by stirring at 105 ° C for 15 hours.

The resulting reaction mixture was cooled to room temperature, added to methanol (80 mL), and stirred at room temperature for 1 hour. Thereafter, filtration was carried out, and the residue was dried under reduced pressure to obtain a red solid (470 mg) containing metal complex M1a.

(Stage 5: synthesis of metal complex M1)

After the reaction vessel was shaded with argon gas atmosphere, the red solid (470 mg), the compound L 1 (210 mg) and the trifluoromethanesulfonic acid (I) (87 mg) containing the metal complex M1a, 2,6 -Lutidine (40 占)) and diethylene glycol dimethyl ether (6.3 ml) were added, and the mixture was stirred at 150 占 폚 for 17 hours.

The resulting reaction mixture was cooled to room temperature, added to methanol (20 mL), and stirred at room temperature for 1 hour. Then, filtration was performed, toluene (20 mL) was added to the residue, and the obtained organic layer was washed with ion-exchanged water. Then, it was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a solid.

The solid was purified by successive purification by recrystallization using a silica gel column chromatography (mixed solvent of toluene and hexane) and a mixed solvent of ethyl acetate and acetonitrile, and then dried under reduced pressure to obtain 200 mg of a metal complex M1 (iridium chloride III ) Yield was 30% based on the amount of IrCl ₃ .3H ₂ O introduced when the hydrate was trihydrate) as a red solid. The HPLC area percentage value of the metal complex M1 was 99.5% or more.

LC-MS (APCI positive): m / z = 2623 [M + H] &lt; ^{+ &}

Example 2 Synthesis of Metal Complex M2

(Stage 1: synthesis of compound L2z)

After the inside of the reaction vessel was put into a nitrogen gas atmosphere, the compound L2y (87.4 g) synthesized according to the method described in JP-A-2012-144721 and tetrahydrofuran (dehydrated product, 870 mL) were added, Lt; / RTI &gt; Thereafter, a hexane solution of n-butyllithium (1.6 mol / L, 100 mL) was added thereto, followed by stirring at -74 ° C for 1 hour. Thereafter, ion-exchanged water (440 mL) was added thereto, the temperature was raised to room temperature, and the solvent was distilled off under reduced pressure. The obtained residue was dissolved in toluene and then washed with ion-exchanged water. Thereafter, the filtrate was dried with anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure to give an oil.

The oil was purified by silica gel column chromatography (hexane) and then dried under reduced pressure to give compound L2z (63.5 g, yield 84%) as a yellow oil. The HPLC area percentage value of compound L2z was 93.0%.

TLC-MS (DART positive): m / z = 502 [M] ^&lt; ⁺ & gt ^;

(Stage 2: synthesis of compound L2a)

After the inside of the reaction vessel was put into a nitrogen gas atmosphere, a mixture of Compound L2z (63.5 g), Compound L1d (35.2 g), [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (3.1 g), 1,1'-bis (diphenylphosphino) ferrocene (2.1 g), potassium acetate (37.1 g) and 1,4-dioxane (370 mL) were added and the mixture was stirred under reflux for 3.5 hours. The resulting reaction mixture was cooled to room temperature, toluene (550 mL) was added, and the mixture was filtered through a filter with silica gel and Celite. After the filtrate was concentrated under reduced pressure, toluene, activated clay and activated charcoal were added, and the mixture was stirred at 60 ° C for 30 minutes, and then filtered through a Celite filter. The filtrate was concentrated under reduced pressure to obtain Compound L2a (78.5 g) as a yellow oily product. The HPLC area percentage value of compound L2a was 89.9%.

TLC-MS (DART positive): m / z = 550 [M] ⁺

(Stage 3: synthesis of compound L2c)

After the inside of the reaction vessel was put in a nitrogen gas atmosphere, Compound L2a (69.4 g), Compound L1b (35.8 g), toluene (760 mL), tert- , Tetrakis (triphenylphosphine) palladium (0) (4.4 g) and a 40 wt% aqueous solution of tetrabutylammonium hydroxide (330 mL) were added and stirred at 50 ° C for 15 hours. After the obtained reaction mixture was cooled to room temperature, toluene was added and the obtained organic layer was washed with ion-exchanged water. Thereafter, the filtrate was dried with anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure to give an oil.

The resulting oil was purified by silica gel column chromatography (mixed solvent of chloroform and hexane), purified by reversed phase silica gel column chromatography (mixed solvent of ethyl acetate and acetonitrile) and dried under reduced pressure to give compound L2c ( 57.2 g, yield 78%) as a colorless oil. The HPLC area percentage value of compound L2c was 99.4%.

TLC-MS (DART positive): m / z = 579 [M] ^&lt; ^{+ &}

(Stage 4: synthesis of compound L2e)

After the inside of the reaction vessel was put in a nitrogen gas atmosphere, a mixture of Compound L2c (56.9 g), Compound L1d (37.3 g), [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (4.8 g), potassium acetate (28.9 g) and 1,2-dimethoxyethane (390 mL) were added and the mixture was stirred for 1.5 hours under reflux. The resulting reaction mixture was cooled to room temperature, toluene (590 mL) was added, and the mixture was filtered through a Celite filter. After the filtrate was concentrated under reduced pressure, hexane and activated charcoal were added, and the mixture was stirred at 65 DEG C for 1 hour and then filtered through a sieve filter. The filtrate was concentrated under reduced pressure to obtain Compound L2e (82.1 g) as a brown oil. The HPLC area percentage value of compound L2e was 98.6%.

LC-MS (APCI positive): m / z = 628 [M + H] &lt; ^{+ &}

(Stage 5: synthesis of compound L2)

The reaction vessel was shaken and the inside of the reaction vessel was put in an argon gas atmosphere. Then, Compound L2e (41.4 g), Compound L1f (30.1 g), tetrakis (triphenylphosphine) palladium (0) (4.6 g), toluene And a tetraethylammonium hydroxide aqueous solution (390 mL) was added thereto, followed by stirring at 70 DEG C for 12 hours. Compound L1f was synthesized according to the method described in JP-A-2008-179617.

After the obtained reaction mixture was cooled to room temperature, toluene was added and the obtained organic layer was washed with ion-exchanged water. Then, it was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a solid.

This solid was purified by silica gel column chromatography (mixed solvent of chloroform and hexane) and purified by reverse phase silica gel column chromatography (mixed solvent of ethyl acetate and acetonitrile), followed by using a mixed solvent of ethyl acetate and methanol And purified by recrystallization. Thereafter, it was dried under reduced pressure at 40 캜 overnight to obtain Compound L2 (45.5 g, yield 82%) as a pale yellow solid. The HPLC area percentage value of compound L2 was 99.2%.

LC-MS (APCI positive): m / z = 845.5 [M + H] &lt;

_{^{1 H-NMR (CD 2 Cl}} 2, 300㎒): δ (ppm) = 9.95 (d, 1H), 9.02 (dd, 1H), 8.70 (dt, 4H), 8.21 (dd, 1H), 8.09 (d (M, 3H), 6.87 (s, 3H), 2.49 (t, 4H), 1.96 s, 3H), 1.58-1.21 (m, 34H), 0.85 (t, 6H).

(Stage 6: synthesis of metal complex M2a)

After the inside of the reaction container shaded was set to an argon gas atmosphere, Compound L2 (376 mg) and 2-ethoxyethanol (30 mL) were added and heated to 80 deg. Thereafter, thereto was added a hydrate of iridium (III) chloride (71 mg) dissolved in ion-exchanged water (10 mL), followed by stirring at 120 ° C for 15 hours.

The obtained reaction mixture was cooled to room temperature, added to methanol (40 mL), and stirred at room temperature for 1 hour. Thereafter, filtration was carried out, and the residue was dried under reduced pressure to obtain a solid (referred to as "solid A", 384 mg) containing the metal complex M2a. By repeating this operation, a required amount of solid A was obtained.

Solid A was purified by silica gel column chromatography (mixed solvent of chloroform and hexane). Thereafter, it was dried under reduced pressure at 50 캜 overnight to obtain a red solid containing metal complex M2a (referred to as &quot; solid B &quot;).

(Stage 7: synthesis of metal complex M2)

Acetyl acetone (260 mg), sodium carbonate (277 mg) and 2-ethoxyethanol (27 mL) were added to the reaction container which had been shaded, and the mixture was stirred at 120 캜 for 3 hours Respectively.

The obtained reaction mixture was cooled to room temperature, toluene (100 mL) was added thereto, and the mixture was washed with ion-exchanged water. Thereafter, the organic layer was dried over anhydrous sodium sulfate, filtered through a filter with silica gel, and the filtrate was concentrated under reduced pressure to obtain a solid.

The solid was purified by washing with ethanol, washing with hexane, and then drying under reduced pressure to obtain the metal complex M2 (320 mg) as a red solid. The HPLC area percentage value of the metal complex M2 was 98.9% or more.

LC-MS (ESI positive): m / z = 2018 [M + K] &lt; ^{+ &}

_{^{1 H-NMR (CD 2 Cl}} 2, 300㎒): δ (ppm) = 9.97 (d, 2H), 9.06 (d, 2H), 9.35 (d, 8H), 8.05 (d, 2H), 7.69 (m 2H), 7.61 (d, 8H), 7.40-7.31 (m, 2H), 7.13 (t, 6H), 6.88-6.81 (m, 8H), 5.48 ), 2.06 (s, 6H), 1.87-1.83 (m, 6H), 1.61-1.40 (m, 44H), 1.26 (m, 24H), 0.89 (m, 12H).

COMPARATIVE EXAMPLE 1 Synthesis of metal complex CM1

The metal complex CM1 was synthesized according to the method described in JP-A-2011-105701.

<Measurement Example 1> Measurement of PLQY and emission spectrum of metal complex M1

PLQY and emission spectrum were measured using a xylene solution (0.0008 wt%) of the metal complex M1. Luminescence having the maximum peak of the luminescence spectrum was observed at 621 nm, and the FWHM of this luminescence spectrum was 36 nm and PLQY was 72%.

<Measurement example 2> Measurement of PLQY and emission spectrum of metal complex M2

PLQY and emission spectrum were measured using a xylene solution (0.0008 wt%) of the metal complex M2. Luminescence having the maximum peak of the luminescence spectrum was observed at 624 nm, and the FWHM of this luminescence spectrum was 65 nm and PLQY was 66%.

<Measurement example C1> Measurement of PLQY and emission spectrum of metal complex CM1

Using a xylene solution (0.0008 wt%) of the metal complex CM1, PLQY and emission spectrum were measured. Luminescence having the maximum peak of the luminescence spectrum was observed at 615 nm, and the FWHM of this luminescence spectrum was 88 nm and PLQY was 53%.

Synthesis Example 1 Synthesis of polymeric compound IP1

The polymer compound IP1 is obtained by reacting the monomer PM1 synthesized according to the method described in JP-A No. 2011-174062 and the monomer PM2 synthesized according to the method described in International Publication No. 2005/049546, and International Publication No. 2002/045184 The monomer PM3 synthesized according to the described method was synthesized by the method described in JP-A-2012-144722 using the monomer PM4 synthesized according to the method described in JP-A-2008-106241.

The polymeric compound IP1 has a constituent unit derived from the monomer PM1, a constituent unit derived from the monomer PM2, a constituent unit derived from the monomer PM3 and a constituent unit derived from the monomer PM4 in the theoretical value obtained from the amount of the input raw material, 50: 30: 12.5: 7.5.

Synthesis Example 2 Synthesis of Compound PM5

Compound PM5a was synthesized according to the method described in International Publication No. 2012/086671.

(Stage 1: synthesis of compound PM5b)

After the inside of the reaction vessel was put into a nitrogen gas atmosphere, 250 g of 4-bromo-n-octylbenzene and tetrahydrofuran (dehydrated product, 2.5 L) were added and cooled to -70 캜 or lower. Thereafter, 2.5 mol / L n-butyllithium-hexane solution (355 mL) was added dropwise thereto, and the mixture was stirred at -70 캜 or lower for 3 hours. Thereafter, a solution prepared by dissolving the compound PM5a (148 g) in tetrahydrofuran (dehydrated product, 400 mL) was added dropwise thereto, the temperature was raised to room temperature, and the mixture was stirred overnight at room temperature. The resulting reaction mixture was cooled to 0 占 폚, and water (150 mL) was added thereto and stirred. The resulting reaction mixture was concentrated under reduced pressure to remove the organic solvent. To the obtained reaction mixture, hexane (1 L) and water (200 mL) were added, and the aqueous layer was removed by separating operation. The obtained organic layer was washed with saturated brine, and dried over magnesium sulfate. The resultant mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the compound PM5b (330 g) as a yellow oil.

(Stage 2: synthesis of compound PM5c)

After the inside of the reaction vessel was put into a nitrogen gas atmosphere, 330 g of the compound PM5b and dichloromethane (900 mL) were added, and the mixture was cooled to 5 캜 or lower. Thereafter, 2.0 mol / L of boron trifluoride diethyl ether complex (245 mL) was added dropwise thereto. Thereafter, the temperature was raised to room temperature, and the mixture was stirred overnight at room temperature. The obtained reaction mixture was added to a vessel containing ice water (2 L), stirred for 30 minutes, and then the water layer was removed. The obtained organic layer was washed once with a potassium phosphate aqueous solution (1 L) at a concentration of 10% by weight, twice with water (1 L), and then dried with magnesium sulfate. The resulting mixture was filtered, and the filtrate was concentrated under reduced pressure to give an oil. The oil was dissolved in toluene (200 mL), and the solution was passed through a filter with silica gel to obtain toluene solution 1. After toluene solution 1 was obtained, toluene (about 3 L) was further passed through a filter with silica gel to obtain toluene solution 2. Toluene solution 1 and toluene solution 2 were mixed and concentrated under reduced pressure to obtain an oily product. Methanol (500 mL) was added to the oil and stirred. The resulting reaction mixture was filtered to obtain a solid. To this solid was added a mixed solvent of butyl acetate and methanol, and the recrystallization was repeated to obtain the compound PM5c (151 g) as a white solid. The HPLC area percentage value of the compound PM5c was 99.0% or more.

^{1 H-NMR (400㎒, CDCl} 3): δ (ppm) = 7.56 (d, 2H), 7.49 (d, 2H), 7.46 (dd, 2H), 7.06 ~ 7.01 (m, 8H), 2.55 (t , 4H), 1.61-1.44 (m, 4H), 1.30-1.26 (m, 20H), 0.87 (t, 6H).

(Stage 3: synthesis of compound PM5)

After the inside of the reaction vessel was put into a nitrogen gas atmosphere, the compound PM5c (100 g) and tetrahydrofuran (dehydrated product, 1000 mL) were added and cooled to -70 캜 or lower. Thereafter, 2.5 mol / L n-butyllithium-hexane solution (126 mL) was added dropwise thereto, and the mixture was stirred at -70 캜 or lower for 5 hours. Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (81 mL) was added dropwise thereto. Thereafter, the temperature was raised to room temperature, and the mixture was stirred overnight at room temperature. The resulting reaction mixture was cooled to -30 占 폚, and a 2.0 mol / L hydrochloric acid-diethyl ether solution (143 mL) was added dropwise. Thereafter, the temperature was raised to room temperature, and the mixture was concentrated under reduced pressure to obtain a solid. Toluene (1.2 L) was added to the solid, and the mixture was stirred at room temperature for 1 hour, and then filtered through a filter with silica gel to obtain a filtrate. The filtrate was concentrated under reduced pressure to obtain a solid. Methanol was added to the solid and stirred, followed by filtration to obtain a solid. This solid was purified by repeating recrystallization using isopropyl alcohol and then dried under reduced pressure at 50 캜 overnight to obtain a compound PM5 (72 g) as a white solid. The HPLC area percentage value of the compound PM5 was 99.0% or more.

^{1 H-NMR (400㎒, CDCl} 3): δ (ppm) = 7.82 (d, 2H), 7.81 (s, 2H), 7.76 (d, 2H), 7.11 (d, 4H), 7.00 (d, 4H ), 2.52 (t, 4H), 1.59-1.54 (m, 4H), 1.36-1.26 (m, 20H), 1.31 (s, 24H), 0.87 (t, 6H).

Synthesis Example 3 Synthesis of Polymer Compound P1

(Stage 1)

After the inside of the reaction vessel was set in an inert gas atmosphere, the monomer PM5 (4.77 g) (the same as the compound PM5), the monomer PM6 (0.773 g) synthesized according to the method described in International Publication No. 2012/086671, the monomer PM3 g), the monomer PM7 (0.331 g) synthesized according to the method described in International Publication No. 2009/131255, the monomer PM8 (0.443 g) synthesized according to the method described in JP 2004-143419 A and toluene ), Which was stirred while heating to 105 ° C.

(Stage 2)

To this was added bistriphenylphosphine palladium dichloride (4.2 mg), followed by dropwise addition of a 20 wt% tetraethylammonium hydroxide aqueous solution (20 mL), followed by stirring under reflux for 3 hours.

(Stage 3)

Thereafter, phenylboronic acid (0.077 g), bistriphenylphosphine palladium dichloride (4.2 mg), toluene (60 mL) and 20 wt% tetraethylammonium hydroxide aqueous solution (20 mL) were added to this, Followed by stirring for 24 hours.

(Stage 4)

After the organic layer was separated from the aqueous layer, N, N-diethyldithiocarbamic acid sodium trihydrate (3.33 g) and ion-exchanged water (67 mL) were added to the obtained organic layer, and the mixture was stirred at 85 캜 for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed twice with ion-exchanged water (78 mL) twice, with 3 wt% acetic acid aqueous solution (78 mL) and twice with ion-exchanged water (78 mL). The organic layer was separated from the aqueous layer, and the organic layer was then added dropwise to methanol to precipitate a solid, which was then filtered and dried to obtain a solid. This solid was dissolved in toluene, and passed through a silica gel column and an alumina column in which toluene had previously passed through. The resulting solution was added dropwise to methanol to precipitate a solid, which was then filtered and dried to obtain a polymer compound P1 (4.95 g). The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer P1 in terms of polystyrene were Mn = 1.4 × 10 ⁵ and Mw = 4.1 × 10 ⁵ .

The polymer compound P1 has a constitutional unit derived from the monomer PM5, a constitutional unit derived from the monomer PM6, a constitutional unit derived from the monomer PM3, a constitutional unit derived from the monomer PM7, And a constituent unit derived from monomer PM8 is composed of a molar ratio of 50: 10: 30: 5: 5.

Example D1 Fabrication and Evaluation of Light Emitting Device D1

(Formation of anode and hole injection layer)

An ITO film was attached to a glass substrate to a thickness of 45 nm by a sputter (sputtering) method to form a cathode. On the anode, polythiophene-sulfonic acid-based hole injecting agent AQ-1200 (manufactured by Plextronics) was formed to a thickness of 65 nm by a spin coating method and heated on a hot plate at 170 DEG C for 15 minutes Thereby forming a hole injection layer.

(Formation of hole transport layer)

The polymer compound IP1 was dissolved in xylene at a concentration of 0.70 wt%. Using the obtained xylene solution, a film having a thickness of 20 nm was formed on the hole injection layer by a spin coating method and heated on a hot plate at 180 캜 for 60 minutes under a nitrogen gas atmosphere to form a hole transporting layer.

(Formation of light emitting layer)

Polymer P1 and metal complex M1 (polymer P1 / metal complex M1 = 92.5% by weight / 7.5% by weight) were dissolved in xylene at a concentration of 1.7% by weight. Using the obtained xylene solution, a film having a thickness of 90 nm was formed on the hole transporting layer by a spin coat method, and the film was heated at 150 캜 for 10 minutes in a nitrogen gas atmosphere to form a light emitting layer.

(Formation of cathode)

The substrate on which the light emitting layer was formed was reduced to 1.0 x 10 &lt; ^-4 &gt; Pa or less in the evaporator, and then the cathode was formed as a negative electrode. About 4 nm of sodium fluoride was deposited on the light emitting layer. After the deposition, the substrate was sealed with a glass substrate to produce the light emitting device D1.

Example D1 Fabrication and Evaluation of Light Emitting Device D1

When a voltage was applied to the light emitting element D1, light emission having the maximum peak of the emission spectrum was observed at 625 nm, and the CIE chromaticity coordinates (x, y) = (0.668, 0.329). The FWHM of this luminescence spectrum was 44 nm. When the light emitting device D1 is used in combination with the color filter shown in Fig. 2, the external quantum efficiency at 1000 cd / m 2 is 12.6%.

Example D2 Fabrication and Evaluation of Light Emitting Device D2

A light emitting device D2 was fabricated in the same manner as in Example D1 except that the polymer P1 and the metal complex M2 were used instead of the polymer P1 and the metal complex M1 in Example D1.

When a voltage was applied to the light emitting element D2, light emission having the maximum peak of the emission spectrum was observed at 625 nm, and the CIE chromaticity coordinates (x, y) = (0.664, 0.333). The FWHM of this luminescence spectrum was 62 nm. When the light emitting element D2 is used in combination with the color filter shown in Fig. 2, the external quantum efficiency at 1000 cd / m 2 is 9.53%.

According to the present invention, it is possible to provide a metal complex excellent in quantum yield and excellent in half width of luminescence spectrum.

Claims (15)

A metal complex represented by the following formula (1).

[Wherein,
M represents an iridium atom or a platinum atom.
n ₁ represents 1, 2 or 3; n ₂ represents 0, 1 or 2; When M is an iridium atom, n ₁ + n ₂ is 3, and when M is a platinum atom, n ₁ + n ₂ is 2.
E ¹ , E ² , E ³ and E ⁴ each independently represent a nitrogen atom or a carbon atom. When there are a plurality of E ¹ , E ² , E ³ and E ⁴ , they may be the same or different. When E ¹ is a nitrogen atom, R ¹ does not exist, and when E ² is a nitrogen atom, R ² does not exist. When E ³ is a nitrogen atom, R ³ does not exist and E ⁴ When it is a nitrogen atom, R ⁴ does not exist.
^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9 and R ¹⁰ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl An aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent. When there are a plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , they may be the same or different. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ^8, and R ⁸ and R ⁹ are each bonded to form a It may form a ring together with an atom. Provided that at least one group selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ is a group represented by the following formula (DA) or (DB).
X ^a and X ^b each independently represent a direct bond, an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Xa ₂ - or NR ^Xa -. R ^Xa represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of R ^Xa , they may be the same or different and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. When ^a plurality of X ^a and X ^b are present, they may be the same or different. Provided that at least one of X ^a and X ^b is an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Xa ₂ - or -NR ^Xa -.
A ¹ -G ¹ -A ² represents an anionic two-dimensional ligand, and G ¹ together with A ¹ and A ² represents an atomic group constituting a two-dimensional ligand. A ¹ and A ² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. When a plurality of A ¹ -G ¹ -A ² exist, they may be the same or different.]

[Wherein,
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
^GDA represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When there are a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , they may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. Multiple ^TTAs present may be the same or different.]

[Wherein,
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more.
^GDA represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent. Multiple ^GDAs may be the same or different.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When Ar ^{DA1, DA2} Ar, Ar ^{DA3, DA4} Ar, Ar ^{DA5, DA6} Ar and Ar ^DA7 a plurality is present, they each may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. Multiple ^TTAs present may be the same or different.] The metal complex according to claim 1, wherein R ² is a group represented by the formula (DA). The metal complex according to claim 1 or 2, wherein the group represented by the formula (DA) is a group represented by the following formula (D-A1), (D-A2) or (D-A3).

[Wherein,
R ^p1 , R ^p2 and R ^p3 each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When there are plural R ^p1 and R ^p2 , they may be the same or different.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. Plural np1 may be the same or different.] The metal complex according to claim 3, wherein the group represented by the formula (D-A) is a group represented by the formula (D-A3). The metal complex according to any one of claims 1 to 4, wherein X ^a is -CR ^Xa ₂ - and X ^b is a direct bond. The metal complex according to any one of claims 1 to 5, wherein E ¹ , E ² , E ³ and E ⁴ are carbon atoms. The metal complex according to any one of claims 1 to 6, wherein M is an iridium atom, n ₁ is 3, and n ₂ is 0. A metal complex represented by the following formula (2).

[Wherein,
M represents an iridium atom or a platinum atom.
n ₁ represents 1, 2 or 3; n ₂ represents 0, 1 or 2; When M is an iridium atom, n ₁ + n ₂ is 3, and when M is a platinum atom, n ₁ + n ₂ is 2.
E ¹ , E ² , E ³ and E ⁴ each independently represent a nitrogen atom or a carbon atom. When there are a plurality of E ¹ , E ² , E ³ and E ⁴ , they may be the same or different. When E ¹ is a nitrogen atom, R ¹¹ is absent. When E ² is a nitrogen atom, R ¹² does not exist. When E ³ is a nitrogen atom, R ¹³ does not exist and E ⁴ When it is a nitrogen atom, R &lt; ¹⁴ &gt; does not exist.
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, An aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent. When there are a plurality of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , they may be the same or different. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ^8, and R ⁸ and R ⁹ are bonded to each other to form a It may form a ring together with an atom.
Y ^a and Y ^b each independently represent a direct bond, an oxygen atom, a sulfur atom, -C (= O) -, -CR ^Ya R ^Yb - or -NR ^Yc -. R ^Ya represents an alkyl group or a cycloalkyl group, and these groups may have an aryl group or a monovalent heterocyclic group as a substituent. R ^Yb represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. R ^Yc represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. Provided that at least one of Y ^a and Y ^b is -CR ^Ya R ^Yb -.
A ¹ -G ¹ -A ² represents an anionic two-dimensional ligand, and G ¹ together with A ¹ and A ² represents an atomic group constituting a two-dimensional ligand. A ¹ and A ² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. When a plurality of A ¹ -G ¹ -A ² exist, they may be the same or different.] The metal complex according to claim 8, wherein Y ^a is -CR ^Ya R ^Yb - and Y ^b is a direct bond. The metal complex according to claim 8 or 9, wherein R ^Ya is an alkyl group which may have a substituent. 11. The metal complex according to any one of claims 8 to 10, wherein R ^Yb is an aryl group which may have a substituent. 12. The metal complex according to claim 11, wherein R ^Yb is a phenyl group which may have a substituent. The compound according to any one of claims 8 to 12, wherein at least one selected from the group consisting of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a group represented by the following formula (DA) or (DB) Metal complex.

[Wherein,
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
^GDA represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When there are a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , they may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. Multiple ^TTAs present may be the same or different.]

[Wherein,
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more.
^GDA represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent. Multiple ^GDAs may be the same or different.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When Ar ^{DA1, DA2} Ar, Ar ^{DA3, DA4} Ar, Ar ^{DA5, DA6} Ar and Ar ^DA7 a plurality is present, they each may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. Multiple ^TTAs present may be the same or different.] A metal complex according to any one of claims 1 to 13,
A composition comprising at least one material selected from the group consisting of a hole transporting material, a hole injecting material, an electron transporting material, an electron injecting material, a light emitting material, an antioxidant and a solvent. A light emitting device obtained by using the metal complex according to any one of claims 1 to 13.

Images